Method for neutral beam processing based on gas cluster ion beam technology and articles produced thereby

ABSTRACT

A method for Neutral Beam irradiation derived from gas cluster ion beams and articles produced thereby including optical elements.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of co-pending InternationalApplication No. PCT/US13/27512, filed on Feb. 22, 2013, entitled METHODFOR NEUTRAL BEAM PROCESSING BASED ON GAS CLUSTER ION BEAM TECHNOLOGY ANDARTICLES PRODUCED THEREBY, which in turn claims priority to and benefitof U.S. Provisional Application No. 61/650,747, filed on May 23, 2012,U.S. Provisional Application No. 61/658,522, filed on Jun. 12, 2012, andU.S. Provisional Application No. 61/601,980, filed on Feb. 22, 2014, thecontents of each of which each incorporated herein by reference for allpurposes.

This application is also a continuation-in-part of co-pending U.S.application Ser. No. 13/215,514, filed on Aug. 23, 2011, entitled METHODAND APPARATUS FOR NEUTRAL BEAM PROCESSING BASED ON GAS CLUSTER ION BEAMTECHNOLOGY, which in turn claims priority to and benefit of U.S.Provisional Application No. 61/484,421, filed on May 10, 2011, U.S.Provisional Application No. 61/473,359, filed on Apr. 8, 2011, U.S.Provisional Application No. 61/490,675, filed on May 27, 2011, and U.S.Provisional Application No. 61/376,225, filed on Aug. 23, 2010, thecontents of each of which each incorporated herein by reference for allpurposes.

FIELD OF THE INVENTION

This invention relates generally to methods and apparatus for lowenergy, Neutral Beam processing and more specifically to high beampurity methods and systems for deriving an accelerated neutral monomerand/or neutral gas cluster beam from an accelerated gas cluster ionbeam. The invention also includes certain new or improved materials anddevices made by the materials.

BACKGROUND OF THE INVENTION

During the past decade, the gas cluster ion beam (GCIB) has become wellknown and widely used for a variety of surface and subsurface processingapplications. Because gas cluster ions typically have a large mass, theytend to travel at relatively low velocities (compared to conventionalions) even when accelerated to substantial energies. These lowvelocities, combined with the inherently weak binding of the clusters,result in unique surface processing capabilities that lead to reducedsurface penetration and reduced surface damage compared to conventionalion beams and diffuse plasmas.

Gas cluster ion beams have been employed to smooth, etch, clean, formdeposits on, grow films on, or otherwise modify a wide variety ofsurfaces including for example, metals, semiconductors, and dielectricmaterials. In applications involving semiconductor andsemiconductor-related materials, GCIBs have been employed to clean,smooth, etch, deposit and/or grow films including oxides and others.GCIBs have also been used to introduce doping and lattice-strainingatomic species, materials for amorphizing surface layers, and to improvedopant solubility in semiconductor materials. In many cases such GCIBapplications have been able to provide results superior to othertechnologies that employ conventional ions, ion beams, and plasmas.Semiconductor materials include a wide range of materials that may havetheir electrical properties manipulated by the introduction of dopantmaterials, and include (without limitation) silicon, germanium, diamond,silicon carbide, and also compound materials comprising group III-IVelements, and group II-VI elements. Because of the ease of forming GCIBsusing argon (Ar) as a source gas and because of the inert properties ofargon, many applications have been developed for processing the surfacesof implantable medical devices such as coronary stents, orthopedicprostheses, and other implantable medical devices using argon gas GCIBs.In semiconductor applications, a variety of source gases and source gasmixtures have been employed to form GCIBs containing electrical dopantsand lattice-straining species, for reactive etching, physical etching,film deposition, film growth, and other useful processes. A variety ofpractical systems for introducing GCIB processing to a wide range ofsurface types are known. For example, U.S. Pat. No. 6,676,989 C1 issuedto Kirkpatrick et al. teaches a GCIB processing system having aworkpiece holder and manipulator suited for processing tubular orcylindrical workpieces such as vascular stents. In another example, U.S.Pat. No. 6,491,800 B2 issued to Kirkpatrick et al. teaches a GCIBprocessing system having workpiece holders and manipulators forprocessing other types of non-planar medical devices, including forexample, hip joint prostheses. A further example, U.S. Pat. No.6,486,478 B1 issued to Libby et al. teaches an automated substrateloading/unloading system suitable for processing semiconductor wafers.U.S. Pat. No. 7,115,511 issued to Hautala, teaches the use of amechanical scanner for scanning a workpiece relative to an un-scannedGCIB, in still another example, U.S. Pat. No. 7,105,199 B2 issued toBlinn et al. teaches the use of GCIB processing to improve the adhesionof drug coatings on medical devices and to modify the elution or releaserate of a drug from the medical devices.

GCIB has been employed in etching and smoothing of crystalline andnon-crystalline forms of materials such as diamonds and other gemstones.This has not been entirely successful in that at times the gemstone mayundergo undesirable color changes as a result of the GCIB processing. Ithas not been clear whether this results from some form of surface orsub-surface damage to the gemstone materials, or might be due to theformation of a roughened interface between the etched and/or smoothedsurface layer resulting from the GCIB processing and the underlyingunmodified bulk of the material, or is perhaps due to damage due tosurface electrical charging induced by the cluster ions. Whatever thecause of the negative side effects of the GCIB processing, a processingtechnique for etching and/or smoothing of natural and synthetic gemstonematerials that does not introduce undesired degradation of theappearance and esthetic appeal of the gems is desirable. GCIB processinghas been indicated as a possible technique for smoothing and/orplanarizing surfaces of optical materials such as lenses, reflectingoptical surfaces, optical windows, optical panels for display andtouch-screen panels, prismatic devices, transparent substrates forphoto-masks and the like, optical waveguides, electro-optical devices,and other optical devices. Materials for optical devices include a widevariety of glasses, quartz, sapphire, diamond, and other hard,transparent materials. Conventional polishing and planarizing includingmechanical, chemical-mechanical, and other techniques have not producedadequate surfaces for the most demanding applications. GCIB processinghas in many cases been shown to be capable of smoothing and/orplanarizing optical surfaces to a degree not obtainable by conventionalpolishing techniques, but alternative techniques that do not result in arough interface between the smoothed surface and the underlying bulkmaterial are needed to avoid creation of scattering layers embedded inthe optical material.

Although GCIB processing has been employed successfully for manyapplications, there are new and existing application needs not fully metby GCIB or other state of the art methods and apparatus. In manysituations, while a GCIB can produce dramatic atomic-scale smoothing ofan initially somewhat rough surface, the ultimate smoothing that can beachieved is often less than the required smoothness, and in othersituations GCIB processing can result in roughening moderately smoothsurfaces rather than smoothing them further.

Other needs/opportunities also exist as recognized and resolved throughembodiments of the present invention. In the field of drug-elutingmedical implants, GCIB processing has been successful in treatingsurfaces of drug coatings on medical implants to bind the coating to asubstrate or to modify the rate at which drugs are eluted from thecoating following implantation into a patient. However, it has beennoted that in some cases where GCIB has been used to process drugcoatings (which are often very thin and may comprise very expensivedrugs), there may occur a weight loss of the drug coating (indicative ofdrug loss or removal) as a result of the GCIB processing. For theparticular cases where such loss occurs (certain drugs and using certainprocessing parameters) the occurrence is generally undesirable andhaving a process with the ability to avoid the weight loss, while stillobtaining satisfactory control of the drug elution rate, is preferable.

In semiconductor applications, GCIBs have been employed with varyingdegrees of success in many surface-processing improvements, howeveropportunities for improvement exist. In conventional GCIB processing,often the result, though significantly improved over earlierconventional technologies, is still not of the quality that is requiredby the most demanding applications. For example, in smoothing processes,for many materials the final degree of smoothness practically obtainableusing GCIB processing does not always meet requirements, in applicationswhere other materials are introduced into semiconductor materials(sometimes called GCIB infusion) for purposes of doping,lattice-straining, and other applications such as film deposition, filmgrowth, and amorphization, the interface between the infused, grown,amorphized, or deposited material often has a roughness ornon-uniformity at the interface between the irradiated layer and theunderlying substrate that impairs optimal performance of theGCIB-modified layer.

Ions have long been favored for many processes because their electriccharge facilitates their manipulation by electrostatic and magneticfields. This introduces great flexibility in processing. However, insome applications, the charge that is inherent to any ion (including gascluster ions in a GCIB) may produce undesirable effects in the processedsurfaces. GCIB has a distinct advantage over conventional ion beams inthat a gas cluster ion with a single or small multiple charge enablesthe transport and control of a much larger mass-flow (a cluster mayconsist of hundreds or thousands of molecules) compared to aconventional ion (a single atom, molecule, or molecular fragment.)Particularly in the case of insulating materials, surfaces processedusing ions often suffer from charge-induced damage resulting from abruptdischarge of accumulated charges, or production of damaging electricalfield-induced stress in the material (again resulting from accumulatedcharges.) In many such cases, GCIBs have an advantage due to theirrelatively low charge per mass, but in some instances may not eliminatethe target-charging problem. Furthermore, moderate to high currentintensity ion beams may suffer from a significant space charge-induceddefocusing of the beam that tends to inhibit transporting a well-focusedbeam over long distances. Again, due to their lower charge per massrelative to conventional ion beams, GCIBs have an advantage, but they donot fully eliminate the space charge transport problem.

A further instance of need or opportunity arises from the fact thatalthough the use of beams of neutral molecules or atoms provides benefitin some surface processing applications and in space charge-free beamtransport, it has not generally been easy and economical to produceintense beams of neutral molecules or atoms except for the case ofnozzle jets, where the energies are generally on the order of a fewmilli-electron-volts per atom or molecule, and thus have limitedprocessing capabilities.

In U.S. Pat. No. 4,935,623 of Hughes Electronics Corporation, Knauer hastaught a method for forming beams of energetic (1 to 10 eV) chargedand/or neutral atoms. Knauer forms a conventional GCIB and directs it atgrazing angles against solid surfaces such as silicon plates, whichdissociates the cluster ions, resulting in as forward-scattered beam ofatoms and conventional ions. This results in an intense but unfocusedbeam of neutral atoms and ions that may be used for processing, or thatfollowing electrostatic separation of the ions may be used forprocessing as a neutral atom beam. By requiring the scattering of theGCIB off of a solid surface to produce dissociation, a significantproblem is introduced by the Knauer techniques. Across a wide range ofbeam energies, a GCIB produces strong sputtering in surfaces that itstrikes. It has been clearly shown (see for example Aoki, T and Matsuo,J, “Molecular dynamics simulations of surface smoothing and sputteringprocess with glancing-angle gas cluster ion beams,” Nucl. Instr. & Meth.in Phys. Research B 257 (2007), pp. 645-648) that even at grazing anglesas employed by Knauer, GCIBs produce considerable sputtering of solids,and thus the forward scattered neutral beam is contaminated by sputteredions and neutral atoms and other particles originating in the solidsurface used for scattering/dissociation. In a multitude of applicationsincluding medical device processing applications and semiconductorprocessing applications, the presence of such sputtered materialcontaminating the forward-scattered beam renders it unsuitable for use.

In U.S. Pat. No. 7,060,989, Swenson et al. teach the use of a gaspressure cell having gas pressure higher than the beam generationpressure to modify the gas cluster ion energy distribution in a GCIB.The technique lowers the energy of gas cluster ions in a GCIB andmodifies some of the surface processing characteristics of such modifiedGCIBs. Such gas modification of GCIB gas cluster ion energy distributionis helpful, but does not reduce problems caused by charges deposited inthe workpiece by the ions in the GCIB and does not solve certainprocessing problems, as for example, the weight loss of drug coatingsduring GCIB processing. Although the techniques of Swenson et al. canimprove the Ultimate surface smoothing characteristics of a GCIB, theresult is still less than ideal.

Gas clusters and gas cluster ion sizes are typically characterized by N,the number of atoms or molecules (depending on whether the gas is atomicor molecular and including variants such as ions, monomers, dimmers,trimers, ligands) comprising the individual cluster. Many of theadvantages contributed by conventional GCIB processing are believed toderive from the low velocities of ions in the GCIB and from the factthat large, loosely bound clusters disintegrate on collision with asolid surface, causing transient heating and pressure but withoutexcessive penetration, implantation, or damage to the substrate beneaththe surface. Effects of such large clusters (having N monomers—asdefined below—on the order of a few thousand or more) are generallylimited to a few tens of Angstroms. However, it has been shown thatsmaller clusters (having N on the order of a few hundred to about athousand) produce more damage to an impacted surface and are capable ofproducing discrete impact craters in a surface (see for example,Houzumi, H., et al. “Scanning tunneling microscopy observation ofgraphite surfaces irradiated with size-selected Ar cluster ion beams”,Jpn. J. Appl. Phys. V44(8), (2005), p 6252 ff). This crater-formingeffect can roughen and remove material from surfaces (etch) inundesirable competition with the surface smoothing effects of the largerclusters. In many other surface processing applications for which GCIBhave been found useful, it is believed that the effects of large gascluster ions and smaller gas cluster ions may compete incounter-productive ways to reduce processing performance. Unfortunately,the readily applied techniques for forming GCIBs all result ingeneration of beams having a broad distribution of cluster sizes havingsize, N, ranging from around 100 to as much as several tens ofthousands. Often the mean and/or peak of the size distribution lies inthe range of from several hundred to a few thousand, with distributiontails gradually diminishing to zero at the size extremes of thedistribution. The cluster-ion size distribution and the mean clustersize, N_(Mean), associated with the distribution is dependent on thesource gas employed and can be significantly influenced by selection ofthe parameters of the nozzle used to form the cluster jet, by thepressure drop through the nozzle, and by the nozzle temperature, allaccording to conventional GCIB formation techniques. Most commercial GMprocessing tools routinely employ magnetic or occasionally electrostaticsize separators to remove the smallest ions and clusters (monomers,dimers, trimers, etc. up to around N=10 or more), which are the mostdamaging. Such filters are often referred to as “monomer filters”,although they typically also remove somewhat larger ions as well as themonomers. Certain electrostatic cluster ion size selectors (as forexample the one employed in U.S. Pat. No. 4,935,623, by Knauer) requireplacing grids of electrical conductors into the beam, which introduces astrong disadvantage due to potential erosion of the grids by the beam,introducing beam contamination while reducing reliability and resultingin the need for additional maintenance to the apparatus. For thatreason, monomer and low-mass filters are now typically of the magnetictype (see for examples, U.S. Pat. No. 6,635,883, to Torti et al. andU.S. Pat. No. 6,486,478, to Libby et al.) Aside from the smallest ions(monomers, dimers, etc.), which are effectively removed by magneticfilters, it appears that most GCIBs contain few or no gas cluster ionsof sizes below about N=100. It may be that such sizes do not readilyform or after forming are not stable. However, clusters in the rangefrom about N=100 to a few hundred seem to be present in the beams ofmost commercial GCIB processing tools. Values of N_(Mean) in the rangeof from a few hundred to several thousand are commonly encountered whenusing conventional techniques. Because, for a given accelerationpotential the intermediate size clusters travel much faster than thelarger clusters, they are more likely to produce craters, roughinterfaces, and other undesirable effects, and probably contribute toless than ideal processing when present in a GCIB.

It is therefore an object of this invention to provide apparatus andmethods for forming high purity neutral gas cluster beams for workpieceprocessing.

It is a further object of this invention to provide apparatus andmethods to provide high purity gas cluster beams that are substantiallyfree of intermediate size clusters.

Yet another object of this invention is to provide apparatus and methodsfor forming high purity, focused, intense beams of neutral atoms ormolecules with energies in the range of from about 1 eV to as much as afew thousand eV.

Still another object of this invention is to provide apparatus andmethods for forming beams capable of improved surface smoothing comparedto conventional GCIBs.

An object of this invention is to provide apparatus and methods forforming doped and/or strained films and/or for introducing foreignatomic species into the surfaces of semiconductor or other materials,wherein the processed surface have interfaces to the underlyingsubstrate material that are superior to those formed using conventionalGCIB processing.

Another object of this invention is to provide apparatus and methods forforming amorphous regions at the surface of a semiconductor or othermaterial using a Neutral Beam and wherein the interface to theunderlying substrate material is superior to one formed usingconventional GCIB processing.

A further object of this invention is to provide apparatus and methodsfor etching surfaces with superior final smoothness as compared toconventional GCIB processing.

A still further object of this invention is to provide apparatus andmethods for etching optical surfaces with superior final smoothness ascompared to conventional GCIB processing.

Another object of this invention is to provide apparatus and methods foradhering an optical coating to an optical surface with adhesion superiorto that obtained by conventional methods.

Another object of this invention is to provide methods for modifying asurface of an optical device to reduce its susceptibility do degradationdue to atmospheric exposure, and to provide optical devices therebyimproved.

A further object of this invention is to provide methods for forming abarrier on a surface of a hygroscopic material to reduce thesusceptibility of the material to absorption of moisture, and to providematerials thereby improved.

Yet another object of this invention is to provide apparatus and methodsfor forming and/or growing films on surfaces of semiconductor and/orother materials, having interfaces to the underlying substrate materialthat are superior to those formed using conventional GCIB processing.

An additional object of this invention is to provide apparatus andmethods for treating electrically insulating materials with NeutralBeams of gas clusters and/or monomers for processing such materialswithout damage induced by beam transported electrical charges.

A further object of this invention is to provide methods for improvingproperties of an optical element or a gem by Neutral Beam irradiation ofa surface of the optical element.

Another object of this invention is to provide an optical element or gemwith improved properties by Neutral Beam technology.

SUMMARY OF THE INVENTION

The objects set forth above as well as further and other objects andadvantages of the present invention are achieved by the variousembodiments of the invention described herein below.

One embodiment of the present invention provides a method of treating asurface of an optical element comprising the steps of providing areduced pressure chamber; forming a gas cluster ion beam comprising gascluster ions within the reduced pressure chamber; accelerating the gascluster ions to form an accelerated gas cluster ion beam along a beampath within the reduced pressure chamber; promoting fragmentation and/ordissociation of at least a portion of the accelerated gas cluster ionsalong the beam path; removing charged particles from the beam path toform an accelerated neutral beam along the beam path in the reducedpressure chamber; holding the optical element in the beam path; treatingat least a portion of a surface of the optical element by irradiating itwith the accelerated neutral beam; and wherein the promoting andremoving steps occur prior to irradiating the surface.

The step of removing may remove essentially all charged particles fromthe beam path. The neutral beam may be substantially free ofintermediate sized clusters. The neutral beam may consist essentially ofgas from the gas cluster ion beam. The step of promoting may includeraising an acceleration voltage in the step of accelerating or improvingionization efficiency in the forming of the gas cluster ion beam. Thestep of promoting may include increasing the range of velocities of ionsin the accelerated gas cluster ion beam. The step of promoting mayinclude introducing one or more gaseous elements used in forming the gascluster ion beam into the reduced pressure chamber to increase pressurealong the beam path. The step of promoting may include increasing thesize of a skimmer aperture used in the step of forming the gas clusterion beam. The step of promoting may include irradiating the acceleratedgas cluster ion beam or the neutral beam with radiant energy. Theneutral beam treating at least a portion of a surface of the workpiecemay consist substantially of monomers having an energy between 1 eV andseveral thousand eV. The method may further comprise the step ofrepositioning the workpiece with a workpiece holder to treat pluralportions of the surface. The method may further comprise the step ofscanning the workpiece with a workpiece holder to treat extendedportions of the surface.

The optical device may comprise any of an electrically insulatingmaterial; a high electrical resistivity material; a crystallinematerial; an amorphous material; a hygroscopic material; a glassmaterial; a gem material; quartz; or a transparent material. Thetreating step may form an optical coating on the optical element.

The treating step may modify an optical property of the optical element.The optical property may be a refractive index. The optical element maybe a gem material. The gem material may be selected from the groupconsisting of diamond, sapphire, quartz, and a synthetic gem material.The optical element may comprise lithium triborate (LBO) and furtherwherein the treating step may form a surface barrier that reducesreactivity or susceptibility to moisture degradation at the surface ofthe LBO.

Another embodiment of the present invention provides a method ofimproving adhesion of an optical coating having a thickness on a surfaceof an optical substrate, comprising the steps of: providing a reducedpressure chamber; forming a gas cluster ion beam comprising gas clusterions within the reduced pressure chamber; accelerating the gas clusterions to form an accelerated gas cluster ion beam along a beam pathwithin the reduced pressure chamber; optionally deriving an acceleratedneutral beam from the accelerated gas cluster ion beam; holding theoptical coating in the beam path or the derived beam path; treating atleast a portion of a surface of the optical coating by irradiating itwith the beam or the derived beam; and wherein the accelerating stepaccelerates by an amount pre-determined to assure that at least aportion of the beam or derived beam penetrates the entire thickness ofthe optical coating to improve adhesion of the coating to the opticalsubstrate.

Yet another embodiment of the present invention provides a method oftreating a hygroscopic crystalline material, comprising the steps of:providing a reduced pressure chamber; forming a gas cluster ion beamcomprising gas cluster ions within the reduced pressure chamber;accelerating the gas cluster ions to form an accelerated gas cluster ionbeam along a beam path within the reduced pressure chamber; optionallyderiving an accelerated neutral beam from the accelerated gas clusterion beam; holding the crystalline material in the beam path or thederived beam path; treating at least a portion of a surface of thecrystalline material by irradiating it with the beam or the derivedbeam; and forming a surface barrier on the crystalline material thatreduces reactivity or susceptibility to moisture degradation at thesurface of the crystalline material.

Still another embodiment of the present invention provides an opticalelement comprising an optical substrate and a surface coating affixed tothe optical substrate by irradiation from a Neutral Beam derived from agas-cluster ion beam. The surface coating may consist of intendedsurface coating materials and atoms of gases used to form the NeutralBeam. The surface coating may consists of intended surface coatingmaterials. Atoms of gases used to form the Neutral Beam may penetratethe surface coating and reach the substrate. Portions of the surfacecoating may be embedded into the optical substrate by the Neutral Beamirradiation. The optical substrate may have an optical property that ismodified by the Neutral Beam irradiation. The optical property may be arefractive index. The optical element may be a gem material. The gemmaterial may be selected from the group consisting of diamond, sapphire,quartz, or a synthetic gem material. The surface coating may be formedby the Neutral Beam irradiation. The optical substrate may behygroscopic and further the surface coating may have improvedhygroscopic properties relative to the optical substrate.

An even further embodiment of the invention provides a hygroscopicsubstrate, comprising a surface coating formed by accelerated NeutralBeam irradiation of the hygroscopic substrate, which surface coating hasimproved hygroscopic properties relative to the hygroscopic substrate.The present invention provides a high beam purity method and system forderiving from an accelerated gas cluster ion beam an accelerated neutralgas cluster and/or preferably monomer beam that can be employed for avariety of types of surface and shallow subsurface materials processingand which is capable, for many applications, of superior performancecompared to conventional GCIB processing. It can provide well-focused,accelerated, intense neutral monomer beams with particles havingenergies in the range of from about 1 eV to as much as a few thousandeV. In this energy range neutral particles can be beneficial ornecessary in many applications, for example when it is desirable tobreak surface or shallow subsurface bonds to facilitate cleaning,etching, smoothing, deposition, amorphization, or to produce surfacechemistry effects, in such cases, energies of from about an eV up to afew thousands of eV per particle can often be useful. This is an energyrange in which it has been impractical with simple, relativelyinexpensive apparatus to form intense neutral beams. In variousembodiments, the accelerated Neutral Beam is employed for a variety ofsurface and shallow subsurface materials processing and to make enhancedmaterials and devices by such processing methods.

These accelerated Neutral Beams are generated by first forming aconventional accelerated GCIB, then partly or essentially fullydissociating it by methods and operating conditions that do notintroduce impurities into the beam, then separating the remainingcharged portions of the beam from the neutral portion, and subsequentlyusing the resulting accelerated Neutral Beam for workpiece processing.Depending on the degree of dissociation of the gas cluster ions, theNeutral Beam produced may be a mixture of neutral gas monomers and gasclusters or may essentially consist entirely or almost entirely ofneutral gas monomers. It is preferred that the accelerated Neutral Beamis an essentially fully dissociated neutral monomer beam.

An advantage of the Neutral Beams that may be produced by the methodsand apparatus of the embodiments of this invention, is that they may beused to process electrically insulating materials without producingdamage to the material due to charging of the surfaces of such materialsby beam transported charges as commonly occurs for all ionized beamsincluding GCIB. For example, in semiconductor and other electronicapplications, ions often contribute to damaging or destructive chargingof thin dielectric films such as oxides, nitrides, etc. The use ofNeutral Beams can enable successful beam processing of polymer,dielectric, and/or other electrically insulating or high resistivitymaterials, coatings, and films in other applications where ion beams mayproduce unacceptable side effects due to surface charging or othercharging effects. Examples include (without limitation) processing ofcorrosion inhibiting coatings, and irradiation cross-linking and/orpolymerization of organic films. In other examples, Neutral Beam inducedmodifications of polymer or other dielectric materials (e.g.sterilization, smoothing, improving surface biocompatibility, andimproving attachment of and/or control of elution rates of drugs) mayenable the use of such materials in medical devices for implant and/orother medical/surgical applications. Further examples include NeutralBeam processing of glass, polymer, and ceramic bio-culture labwareand/or environmental sampling surfaces where such beams may be used toimprove surface characteristics like, for example, roughness,smoothness, hydrophilicity, and biocompatibility.

Since the parent GCIB, from which accelerated Neutral Beams may beformed by the methods and apparatus of embodiments of the invention,comprises ions, it is readily accelerated to desired energy and isreadily focused using conventional ion beam techniques. Upon subsequentdissociation and separation of the charged ions from the neutralparticles, the Neutral Beam particles tend to retain their focusedtrajectories and may be transported for extensive distances with goodeffect.

When neutral gas clusters in a jet are ionized by electron bombardment,they become heated and/or excited. This may result in subsequentevaporation of monomers from the ionized gas cluster, afteracceleration, as it travels down the beamline. Additionally, collisionsof gas cluster ions with background gas molecules in the ionizer,accelerator and hemline regions, also heat and excite the gas clusterions and may result in additional subsequent evolution of monomers fromthe gas cluster ions following acceleration. When these mechanisms forevolution of monomers are induced by electron bombardment and/orcollision with background gas molecules (and/or other gas clusters) ofthe same gas from which the GCIB was formed, no contamination iscontributed to the beam by the dissociation processes that results inevolving the monomers.

There are other mechanisms that can be employed for dissociating (orinducing evolution of monomers from) gas cluster ions in a GCIB withoutintroducing contamination into the beam. Some of these mechanisms mayalso be employed to dissociate neutral gas clusters in a neutral gascluster beam. One mechanism is laser irradiation of the cluster-ion beamusing infra-red or other laser energy. Laser-induced heating of the gascluster ions in the laser irradiated GCIB results in excitement and/orheating of the gas cluster ions and causes subsequent evolution ofmonomers from the beam. Another mechanism is passing the beam through athermally heated tube so that radiant thermal energy photons impact thegas cluster ions in beam. The induced heating of the gas cluster ions bythe radiant thermal energy in the tube results in excitement and/orheating of the gas cluster ions and causes subsequent evolution ofmonomers from the beam. In another mechanism, crossing the gas clusterion beam by a gas jet of the same gas or mixture as the source gas usedin formation of the GCIB (or other non-contaminating gas) results incollisions of monomers of the gas in the gas jet with the gas clustersin the ion beam producing excitement and/or heating of the gas clusterions in the beam and subsequent evolution of monomers from the excitedgas cluster ions. By depending entirely on electron bombardment duringinitial ionization and/or collisions (with other cluster ions, or withbackground gas molecules of the same gas(es) as those used to form theGCIB) within the beam and/or laser or thermal radiation and/or crossedjet collisions of non-contaminating gas to produce the GCIB dissociationand/or fragmentation, contamination of the beam by collision with othermaterials is avoided.

Through the use of such non-contaminating methods of dissociationdescribed above, the GCIB is dissociated or at least partiallydissociated without introducing atoms to the dissociation products orresidual clusters that are not part of the original source gas atoms. Byusing a source gas for initial cluster formation that does not containatoms which would be contaminants for the workpiece to be processedusing the residual clusters or dissociation products, contamination ofthe workpiece is avoided. When argon or other noble gases are employed,the source gas materials are volatile and not chemically reactive, andupon subsequent irradiation of the workpiece using Neutral Beams thesevolatile non-reactive atoms are fully released from the workpiece. Thusfor workpieces that are optical and gem materials including glasses,quartz, sapphire, diamond, and other hard, transparent materials such aslithium triborate (LBO), argon and other noble gases can serve as sourcegas materials without contributing contamination due to Neutral Beamirradiation. In other cases, other source gases may be employed,provided the source gas atomic constituents do not include atoms thatwould result in contamination of the workpiece. For example, for someglass workpieces, LBO, and various other optical materials are oxygencontaining, and oxygen atoms may not serve as contaminants. In suchcases oxygen-containing source gases may be employed withoutcontamination.

As a neutral gas cluster jet from a nozzle travels through an ionizingregion where electrons are directed to ionize the clusters, a clustermay remain un-ionized or may acquire a charge state, q, of one or morecharges (by ejection of electrons from the cluster by an incidentelectron). The ionizer operating conditions influence the likelihoodthat a gas cluster will take on a particular charge state, with moreintense ionizer conditions resulting in greater probability that ahigher charge state will be achieved. More intense ionizer conditionsresulting in higher ionization efficiency may result from higherelectron flux and/or higher (within limits) electron energy. Once thegas cluster has been ionized, it is typically extracted from theionizer, focused into a beam, and accelerated by falling through anelectric field. The amount of acceleration of the gas cluster ion isreadily controlled by controlling the magnitude of the acceleratingelectric field. Typical commercial GCIB processing tools generallyprovide for the gas cluster ions to be accelerated by an electric fieldhaving an adjustable accelerating potential, V_(Acc), typically of, forexample, from about 1 kV to 70 kV (but not limited to that range−V_(Acc) up to 200 kV or even more may be feasible). Thus a singlycharged gas cluster ion achieves an energy in the range of from 1 to 70keV (or more if larger V_(Acc) is used) and a multiply charged (forexample, without limitation, charge state, q=3 electronic charges) gascluster ion achieves an energy in the range of from 3 to 210 keV (ormore for higher V_(Acc)). For other gas cluster ion charge states andacceleration potentials, the accelerated energy per cluster is qV_(Acc)eV. From a given ionizer with a given ionization efficiency, gas clusterions will have a distribution of charge states from zero (not ionized)to a higher number such as for example 6 (or with high ionizerefficiency, even more), and the most probable and mean values of thecharge state distribution also increase with increased ionizerefficiency (higher electron flux and/or energy). Higher ionizerefficiency also results in increased numbers of gas cluster ions beingformed in the ionizer. In many cases, GCIB processing throughputincreases when operating the ionizer at high efficiency results inincreased GCIB current. A downside of such operation is that multiplecharge states that may occur on intermediate size gas cluster ions canincrease crater and/or rough interface formation by those ions, andoften such effects may operate counterproductively to the intent of theprocessing. Thus for many GCIB surface processing recipes, selection ofthe ionizer operating parameters tends to involve more considerationsthan just maximizing beam current. In some processes, use of a “pressurecell” (see U.S. Pat. No. 7,060,989, to Swenson et al.) may be employedto permit operating an ionizer at high ionization efficiency while stillobtaining acceptable beam processing performance by moderating the beamenergy by gas collisions in an elevated pressure “pressure cell.”

When the Neutral Beams are formed in embodiments of the presentinvention there is no downside to operating the ionizer at highefficiency—in fact such operation is sometimes preferred. When theionizer is operated at high efficiency, there may be a wide range ofcharge states in the gas cluster ions produced by the ionizer. Thisresults in a wide range of velocities in the gas cluster ions in theextraction region between the ionizer and the accelerating electrode,and also in the downstream beam. This may result in an enhancedfrequency of collisions between and among gas cluster ions in the beamthat generally results in a higher degree of fragmentation of thelargest gas cluster ions. Such fragmentation may result in aredistribution of the cluster sizes in the beam, skewing it toward thesmaller cluster sizes. These cluster fragments retain energy inproportion to their new size (N) and so become less energetic whileessentially retaining the accelerated velocity of the initialunfragmented gas cluster ion. The change of energy with retention ofvelocity following collisions has been experimentally verified (as forexample reported in Toyoda, N. et al., “Cluster size dependence onenergy and velocity distributions of gas cluster ions after Collisionswith residual gas,” Nucl. Instr. & Meth. in Phys. Research B 257 (2007),pp 662-665). Fragmentation may also result in redistribution of chargesin the cluster fragments. Some uncharged fragments likely result andmulti-charged gas cluster ions may fragment into several charged gascluster ions and perhaps some uncharged fragments. It is understood bythe inventors that design of the focusing fields in the ionizer and theextraction region may enhance the focusing of the smaller gas clusterions and monomer ions to increase the likelihood of collision withlarger gas cluster ions in the beam extraction region and in thedownstream beam, thus contributing to the dissociation and/orfragmenting of the gas cluster ions.

In an embodiment of the present invention, background gas pressure inthe ionizer, acceleration region, and beamline may optionally bearranged to have a higher pressure than is normally utilized for goodGCIB transmission. This can result in additional evolution of monomersfrom gas cluster ions (beyond that resulting from the heating and/orexcitement resulting from the initial gas cluster ionization event).Pressure may be arranged so that gas cluster ions have a short enoughmean-free-path and a long enough flight path between ionizer andworkpiece that they must undergo multiple collisions with background gasmolecules.

For a homogeneous gas cluster ion containing N monomers and having acharge state of q and which has been accelerated through an electricfield potential drop of V_(Acc) volts, the cluster will have an energyof approximately qV_(Acc)/N₁ eV per monomer, where N₁ is the number ofmonomers in the cluster ion at the time of acceleration. Except for thesmallest gas cluster ions, a collision of such an ion with a backgroundgas monomer of the same gas as the cluster source gas will result inadditional deposition of approximately of qV_(Acc)/N₁ eV into the gascluster ion. This energy is relatively small compared to the overall gascluster ion energy (qV_(Acc)) and generally results in excitation orheating of the cluster and in subsequent evolution of monomers from thecluster. It is believed that such collisions of larger clusters withbackground gas seldom fragment the cluster but rather heats and/orexcites it to result in evolution of monomers by evaporation or similarmechanisms. Regardless of the source of the excitation that results inthe evolution of a monomer or monomers from a gas cluster ion, theevolved monomer(s) have approximately the same energy per particle,qV_(Acc)/N₁ eV, and retain approximately the same velocity andtrajectory as the gas cluster ion from which they have evolved. Whensuch monomer evolutions occur from a gas cluster ion, whether theyresult from excitation or heating due to the original ionization event,a collision, or radiant heating, the charge has a high probability ofremaining with the larger residual gas cluster ion. Thus after asequence of monomer evolutions, a large gas cluster ion may be reducedto a cloud of co-traveling monomers with perhaps a smaller residual gascluster ion (or possibly several if fragmentation has also occurred).The co-traveling monomers following the original beam trajectory allhave approximately the same velocity as that of the original gas clusterion and each has energy of approximately qV_(Acc)/N₁ eV. For small gascluster ions, the energy of collision with a background gas monomer islikely to completely and violently dissociate the small gas cluster andit is uncertain whether in such cases the resulting monomers continue totravel with the beam or are ejected from the beam.

To avoid contamination of the beam by collisions with the backgroundgas, it is preferred that the background gas be the same gas as the gasconstituting the gas cluster ions. Nozzles for forming gas cluster jetsare typically operated with high gas flow on the order of 100-600 sccm.The portion of this flow that does not condense into gas clusters raisesthe pressure in the source chamber. In addition to the gas transmittedthrough the skimmer aperture in the form of gas clusters, unclusteredsource gas from the source chamber can flow through the skimmer apertureto the downstream beamline or beam path chamber(s). Selecting theskimmer aperture diameter to provide an increased flow of unclusteredsource gas from the source chamber to the beamline is a convenient wayto provide the added beamline pressure to induce background gascollisions with the GCIB. Because of the high source gas flow(unclustered gas through the skimmer aperture and gas transported to thetarget by the beam) atmospheric, gases are quickly purged from thebeamline. Alternatively, gas may be leaked into the beamline chamber, oras pointed out above, introduced as a jet crossing the GCIB path. Insuch case, the gas is preferably the same as the source gas (or inert orotherwise non-contaminating). In critical applications a residual gasanalyzer can be employed in the beamline to confirm the quality of thebackground gas, when background gas collisions play a role in theevolution of monomers.

Prior to the GCIB reaching the workpiece, the remaining chargedparticles (gas cluster ions, particularly small and intermediate sizegas cluster ions and some charged monomers, but also including anyremaining large gas cluster ions) in the beam are separated from theneutral portion of the beam, leaving only a Neutral Beam for processingthe workpiece.

In typical operation, the fraction of power in the Neutral Beam relativeto that in the full (charged plus neutral) beam delivered at theprocessing target is in the range of from about 5% to 95%, so by theseparation methods and apparatus disclosed herein it is possible todeliver that portion of the kinetic energy of the full acceleratedcharged beam to the target as a Neutral Beam.

The dissociation of the gas cluster ions and thus the production of highneutral monomer beam energy is facilitated by:

1) Operating at higher acceleration voltages. This increases qV_(Acc)/Nfor any given cluster size; 2) Operating at high ionizer efficiency.This increases qV_(Acc)/N for any given cluster size by increasing q andincreases cluster-ion on cluster-ion collisions in the extraction regiondue to the differences in charge states between clusters; 3) Operatingat a high ionizer, acceleration region, or beamline pressure oroperating with a gas jet crossing the beam, or with a longer beam path,all of which increase the probability of background gas collisions for agas cluster ion of any given size; 4) Operating with laser irradiationor thermal radiant heating of the beam, which directly promote evolutionof monomers from the gas cluster ions; and

5) Operating at higher nozzle gas flow, which increases transport ofgas, clustered and perhaps clustered into the GCIB trajectory, whichincreases collisions resulting in greater evolution of monomers.

For producing background gas collisions, the product of the gas clusterion beam path length from extraction region to workpiece times thepressure in that region contributes to the degree of dissociation of thegas cluster ions that occurs. For 30 kV acceleration, ionizer parametersthat provide a mean gas cluster ion charge state of 1 or greater, and apressure times beam path length of 6×10⁻³ torr-cm (0.8 pascal-cm) (at 25deg C.) provides a Neutral Beam (after separation from the residualcharged ions) that is essentially fully dissociated to neutral energeticmonomers. It is convenient and customary to characterize the pressuretimes beam path length as a gas target thickness. 6×10⁻³ torr-cm (0.8pascal-cm) corresponds to a gas target thickness of approximately1.94×10¹⁴ gas molecules/cm². In one exemplary (not for limitation)embodiment the background gas pressure is 6×10⁻⁵ torr (8×10⁻³ pascal)and the beam path length is 100 cm, the acceleration potential is 30 kV,and in this case the Neutral Beam is observed to be essentially fullydissociated into monomers at the end of the beam path. This is withoutlaser or radiant beam heating and without employing a gas jet crossingthe beam. The fully dissociated accelerated Neutral Beam conditionresults from monomer evolution from cluster heating due to the clusterionization event, collisions with residual gas monomers, and collisionsbetween clusters in the beam.

Using the dissociated Neutral Beam produces improved smoothing resultson smoothing a gold film compared to the full beam. In anotherapplication, using the dissociated Neutral Beam on a drug surfacecoating on a medical device, or on drug-polymer-mixture layer on amedical device or on a drug-poly-mixture body of a medical deviceprovides improved drug attachment and modification of a drug elutionrate without the drug weight loss that occurs when the full GCIB isused.

Measurement of the Neutral Beam cannot be made by current measurement asis convenient for gas cluster ion beams. A Neutral Beam power sensor isused to facilitate dosimetry when irradiating a workpiece with a NeutralBeam. The Neutral Beam sensor is a thermal sensor that intercepts thebeam (or optionally a known sample of the beam). The rate of rise oftemperature of the sensor is related to the energy flux resulting fromenergetic beam irradiation of the sensor. The thermal measurements mustbe made over a limited range of temperatures of the sensor to avoiderrors due to thermal re-radiation of the energy incident on the sensor.For a GCIB process, the beam power (watts) is equal to the beam current(amps) times V_(Acc), the beam acceleration voltage. When a GCIBirradiates a workpiece for a period of time (seconds), the energy(joules) received by the workpiece is the product of the beam power andthe irradiation time. The processing effect of such a beam when itprocesses an extended area is distributed over the area (for example,cm²). For ion beams, it has been conveniently conventional to specify aprocessing dose in terms of irradiated ions/cm², where the ions areeither known or assumed to have at the time of acceleration an averagecharge state, q, and to have been accelerated through a potentialdifference of V_(Acc) volts, so that each ion carries an energy of qV_(Acc) eV (an eV is approximately 1.6×10⁻¹⁹ joule). Thus an ion beamdose for an average charge state, q, accelerated by V_(Acc) andspecified in ions/cm² corresponds to a readily calculated energy doseexpressible in joules/cm². For an accelerated Neutral Beam derived froman accelerated GCM as utilized in embodiments of the present invention,the value of q at the time of acceleration and the value of V_(Acc) isthe same for both of the (later-formed and separated) charged anduncharged fractions of the beam. The power in the two (neutral andcharged) fractions of the UCIB divides proportional to the mass in eachbeam fraction. Thus for the accelerated Neutral Beam as employed inembodiments of the invention, when equal areas are irradiated for equaltimes, the energy dose (joules/cm²) deposited by the Neutral Beam isnecessarily less than the energy dose deposited by the full GCIB. Byusing a thermal sensor to measure the power in the full GCIB, P_(G), andthat in the Neutral Beam, P_(N), (which is commonly found to be fromabout 5% to about 95% that of the full GCIB) it is possible to calculatea compensation factor for use in the Neutral Beam processing dosimetry.When P_(N) is equal to aP_(G), then the compensation factor is, k=1/a.Thus if a workpiece is processed using a Neutral Beam derived from aGCIB, for a time duration is made to be k times greater than theprocessing duration for the full GCIB (including charged and neutralbeam portions) required to achieve a dose of D ions/cm², then the energydoses deposited in the workpiece by both the Neutral Beam and the fullGCIB are the same (though the results may be different due toqualitative differences in the processing effects due to differences ofparticle sizes in the two beams.) As used herein, a Neutral Beam processdose compensated in this way is sometimes described as having anenergy/cm² equivalence of a dose of D ions/cm².

Use of a Neutral Beam derived from a gas cluster ion beam in combinationwith a thermal power sensor for dosimetry in many cases has advantagescompared with the use of the full gas cluster ion beam or an interceptedor diverted portion, which inevitably comprises a mixture of gas clusterions and neutral gas clusters and/or neutral monomers, and which isconventionally measured for dosimetry purposes by using a beam currentmeasurement. Some advantages are as follows:

1) The dosimetry can be more precise with the Neutral Beam using athermal sensor for dosimetry because the total power of the beam ismeasured. With a GCIB employing the traditional beam current measurementfor dosimetry, only the contribution of the ionized portion of the beamis measured and employed for dosimetry. Minute-to-minute andsetup-to-setup changes to operating conditions of the GCIB apparatus mayresult in variations in the fraction of neutral monomers and neutralclusters in the GCIB. These variations can result in process variationsthat may be less controlled when the dosimetry is done by beam currentmeasurement.

2) With a Neutral Beam, a wide variety of materials may be processed,including highly insulating materials and other materials that may bedamaged by electrical charging effects, without the necessity ofproviding a source of target neutralizing electrons to prevent workpiececharging due to charge transported to the workpiece by an ionized beam.When employed with conventional GCIB, target neutralization to reducecharging is seldom perfect, and the neutralizing electron source itselfoften introduces problems such as workpiece heating, contamination fromevaporation or sputtering in the electron source, etc. Since a NeutralBeam does not transport charge to the workpiece, such problems arereduced.

3) There is no necessity for an additional device such as a largeaperture high strength magnet to separate energetic monomer ions fromthe Neutral Beam. In the case of conventional GCIB the risk of energeticmonomer ions (and other small cluster ions) being transported to theworkpiece, where they penetrate producing deep damage, is significantand an expensive magnetic filter is routinely required to separate suchparticles from the beam. In the case of the Neutral Beam apparatusdisclosed herein, the separation of all ions from the beam to producethe Neutral Beam inherently removes all monomer ions.

As used herein, the term “drug” is intended to mean a therapeutic agentor a material that is active in a generally beneficial way, which can bereleased or eluted locally in the vicinity of an implantable medicaldevice to facilitate implanting (for example, without limitation, byproviding lubrication) the device, or to facilitate (for example,without limitation, through biological or biochemical activity) afavorable medical or physiological outcome of the implantation of thedevice. The meaning of “drug” is intended to include a mixture of a drugwith a polymer that is employed for the purpose of binding or providingcoherence to the drug, attaching the drug to the medical device, or forforming a barrier layer to control release or elution of the drug. Adrug that has been modified by ion beam irradiation to density,carbonize or partially carbonize, partially denature, cross-link orpartially cross-link, or to at least partially polymerize molecules ofthe drug is intended to be included in the “drug” definition.

As used herein, the term “intermediate size”, when referring to gascluster size or gas cluster ion size is intended to mean sizes of fromN=10 to N=1500.

As used herein, the terms “GCIB”, “gas cluster ion beam” and “gascluster ion” are intended to encompass not only ionized beams and ions,but also accelerated beams and ions that have had all or a portion oftheir charge states modified (including neutralized) following theiracceleration. The terms “GCIB” and “gas cluster ion beam” are intendedto encompass all beams that comprise accelerated gas clusters eventhough they may also comprise non-clustered particles. As used herein,the term “Neutral Beam” is intended to mean a beam of neutral gasclusters and/or neutral monomers derived from an accelerated gas dusterion beam and wherein the acceleration results from acceleration of a gasduster ion beam.

As used herein in referencing a particle in a gas or a particle in abeam, the term “monomer” refers equally to either a single atom or asingle molecule. The terms “atom,” “molecule,” and “monomer” may be usedinterchangeably and all refer to the appropriate monomer that ischaracteristic of the gas under discussion (either a component of acluster, a component of a duster ion, or an atom or molecule). Forexample, a monatomic gas like argon may be referred to in terms ofatoms, molecules, or monomers and each of those terms means a singleatom. Likewise, in the case of a diatomic gas like nitrogen, it may bereferred to in terms of atoms, molecules, or monomers, each term meaninga diatomic molecule. Furthermore a molecular gas like CO₂ or B₂H₆, maybe referred to in terms of atoms, molecules, or monomers, each termmeaning a polyatomic molecule. These conventions are used to simplifygeneric discussions of gases and gas clusters or gas cluster ionsindependent of whether they are monatomic, diatomic, or molecular intheir gaseous form. In referring to a constituent of a molecule or of asolid material, “atom” has its conventional meaning.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the present invention, together with otherand further objects thereof, reference is made to the accompanyingdrawings, wherein:

FIG. 1 is a schematic illustrating elements of a prior art apparatus forprocessing a workpiece using a GM;

FIG. 2 is a schematic illustrating elements of another prior artapparatus for workpiece processing using a GCIB, wherein scanning of theion beam and manipulation of the workpiece is employed;

FIG. 3 is a schematic of an apparatus according to an embodiment of theinvention, which uses electrostatic deflection plates to separate thecharged and uncharged beam components;

FIG. 4 is a schematic of an apparatus according to the an embodiment ofthe invention, using a thermal sensor for Neutral Beam measurement;

FIG. 5 is a schematic of an apparatus according to an embodiment of theinvention which uses deflected ion beam current collected on asuppressed deflection plate as a component of a dosimetry scheme;

FIG. 6 is a schematic of an apparatus according to an embodiment of theinvention which uses a sample of the deflected ion beam collected in afaraday cup as a component of a dosimetry scheme;

FIG. 7 shows a schematic of an apparatus according to an embodiment ofthe invention, employing mechanical scanning for irradiating an extendedworkpiece uniformly with a Neutral Beam;

FIG. 8 shows a schematic of an apparatus according to an embodiment ofthe invention with means for controlling the gas target thickness byinjecting gas into the beamline chamber;

FIG. 9 shows a schematic of an apparatus according to an embodiment ofthe invention, which uses an electrostatic mirror to separate chargedand neutral beam components;

FIG. 10 shows a schematic of an apparatus according to an embodiment ofthe invention wherein an accelerate-decelerate configuration is used toseparate the charged beam from the neutral beam components;

FIG. 11 shows a schematic of an apparatus according to an embodiment ofthe invention wherein an alternate accelerate-decelerate configurationis used to separate the charged beam from the neutral beam components;

FIGS. 12A, 12B, 12C, and 12D show processing results indicating that fora metal film, processing by a neutral component of a beam producessuperior smoothing of the film compared to processing with either a fullGCIB or a charged component of the beam;

FIGS. 13A and 13B show comparison of a drug coating on a cobalt-chromecoupon representing a drug eluting medical device, wherein processingwith a Neutral Beam produces a superior result to processing with a fullGCIB;

FIG. 14 is a schematic of a Neutral Beam processing apparatus accordingto an embodiment of the invention wherein magnetic separation isemployed;

FIGS. 15A, 15B, and 15C are TEM images illustrating the superiorinterfaces produced when using Neutral Beam embodiments of the inventionas compared to gas cluster ion beams;

FIG. 16 is a graph showing a SIMS profile of a shallow boronimplantation suitable for forming shallow junctions, using an embodimentof the invention;

FIG. 17 is a TEM image showing a high quality interface formed when anembodiment of the invention is used in forming a boron dopedsemiconductor;

FIG. 18 is a graph illustrating the etching of SiO₂ and Si using anembodiment of the invention;

FIGS. 19A and 19B are TEM images illustrating the use of embodiments ofthe invention in forming amorphous layers in semiconductor materials;

FIGS. 20A and 20B are TEM images illustrating the application ofaccelerated Neutral Beams derived from GCIBs for forming films insemiconductors;

FIG. 21 is a graph illustrating the deposition of a diamond-like carbonfilm on a silicon substrate using an accelerated Neutral Beam derivedfrom an accelerated GCIB;

FIG. 22 is an atomic force micrograph map of roughness of a clean,conventionally polished optical glass surface, showing a degree ofroughness, lack of planarity, and the presence of asperities;

FIG. 23 is an atomic force micrograph map of an optical glass surfaceafter smoothing according to an embodiment of the invention using anaccelerated Neutral Beam derived from an accelerated GCIB;

FIGS. 24A, 24B, 24C, and 24D are schematics that show steps in a processfor using an accelerated Neutral Beam derived from a GCIB or for using aGCIB for producing an optical coating on an optical substrate withsuperior adhesion of the coating to the substrate according to anembodiment of the invention as compared with conventional techniques;

FIGS. 25A and 25B are atomic force micrograph maps of surfaces of anuntreated LBO optical component showing degradation due to atmosphericexposure; and

FIGS. 26A and 26B are atomic force micrograph maps of surfaces of an LBOoptical component treated using an accelerated Neutral Beam derived froma GCIB, with resulting reduced degradation due to atmospheric exposurefollowing treatment according to an embodiment of the invention.

DETAILED DESCRIPTION OF THE DRAWINGS

Reference is now made to FIG. 1, which shows a schematic configurationfor a prior art GCIB processing apparatus 100. A low-pressure vessel 102has three fluidly connected chambers: a nozzle chamber 104, anionization/acceleration chamber 106, and as processing chamber 108. Thethree chambers are evacuated by vacuum pumps 146 a, 146 b, and 146 c,respectively. A pressurized condensable source gas 112 (for exampleargon) stored in a gas storage cylinder 111 flows through a gas meteringvalve 113 and a feed tube 114 into a stagnation chamber 116. Pressure(typically a few atmospheres) in the stagnation chamber 116 results inejection of gas into the substantially lower pressure vacuum through anozzle 110, resulting in formation of a supersonic gas jet 118. Cooling,resulting from the expansion in the jet, causes a portion of the gas jet118 to condense into clusters, each consisting of from several toseveral thousand weakly bound atoms or molecules. A gas skimmer aperture120 is employed to control flow of gas into the downstream chambers bypartially separating gas molecules that have not condensed into acluster jet from the cluster jet. Excessive pressure in the downstreamchambers can be detrimental by interfering with the transport of gascluster ions and by interfering with management of the high voltagesthat may be employed for beam formation and transport. Suitablecondensable source gases 112 include, but are not limited to argon andother condensable noble gases, nitrogen, carbon dioxide, oxygen, andmany other gases and/or gas mixtures. After formation of the gasclusters in the supersonic gas jet 118, at least a portion of the gasclusters are ionized in an ionizer 122 that is typically an electronimpact ionizer that produces electrons by thermal emission from one ormore incandescent filaments 124 (or from other suitable electronsources) and accelerates and directs the electrons, enabling them tocollide with gas clusters in the gas jet 118. Electron impacts with gasclusters eject electrons from some portion of the gas clusters, causingthose clusters to become positively ionized. Some clusters may have morethan one electron ejected and may become multiply ionized. Control ofthe number of electrons and their energies after acceleration typicallyinfluences the number of ionizations that may occur and the ratiobetween multiple and single ionizations of the gas clusters. Asuppressor electrode 142, and grounded electrode 144 extract the clusterions from the ionizer exit aperture 126, accelerate them to a desiredenergy (typically with acceleration potentials of from several hundred Vto several tens of kV), and focuses them to form a GCIB 128. The regionthat the GCIB 128 traverses between the ionizer exit aperture 126 andthe suppressor electrode 142 is referred to as the extraction region.The axis (determined at the nozzle 110), of the supersonic gas jet 118containing gas clusters is substantially the same as the axis 154 of theGCIB 128. Filament power supply 136 provides filament voltage V_(f) toheat the ionizer filament 124. Anode power supply 134 provides anodevoltage V_(A) to accelerate thermoelectrons emitted from filament 124 tocause the thermoelectrons to irradiate the cluster-containing gas jet118 to produce cluster ions. A suppression power supply 138 suppliessuppression voltage V_(S) (on the order of several hundred to a fewthousand volts) to bias suppressor electrode 142. Accelerator powersupply 140 supplies acceleration voltage V_(Acc) to bias the ionizer 122with respect to suppressor electrode 142 and grounded electrode 144 soas to result in a total GCIB acceleration potential equal to V_(Acc).Suppressor electrode 142 serves to extract ions from the ionizer exitaperture 126 of ionizer 122 and to prevent undesired electrons fromentering the ionizer 122 from downstream, and to form a focused GCIB128.

A workpiece 160, which may (for example) be a medical device, asemiconductor material, an optical element, or other workpiece to beprocessed by GCIB processing, is held on a workpiece holder 162, thatdisposes the workpiece in the path of the GCIB 128. The workpiece holderis attached to but electrically insulated from the processing chamber108 by an electrical insulator 164. Thus, GCIB 128 striking theworkpiece 160 and the workpiece holder 162 flows through an electricallead 168 to a dose processor 170. A beam gate 172 controls transmissionof the GCIB 128 along axis 154 to the workpiece 160. The beam gate 172typically has an open state and a closed state that is controlled by alinkage 174 that may be (for example) electrical, mechanical, orelectromechanical. Dose processor 170 controls the open/closed state ofthe beam gate 172 to manage the GCIB dose received by the workpiece 160and the workpiece holder 162. In operation, the dose processor 170 opensthe beam gate 172 to initiate GCIB irradiation of the workpiece 160.Dose processor 170 typically integrates GCIB electrical current arrivingat the workpiece 160 and workpiece holder 162 to calculate anaccumulated GCIB irradiation dose. At a predetermined dose, the doseprocessor 170 closes the beam gate 172, terminating processing when thepredetermined dose has been achieved.

In the following description, for simplification of the drawings, itemnumbers from earlier figures may appear in subsequent figures withoutdiscussion. Likewise, items discussed in relation to earlier figures mayappear in subsequent figures without item numbers or additionaldescription. In such cases items with like numbers are like items andhave the previously described features and functions and illustration ofitems without item numbers shown in the present figure refer to likeitems having the same functions as the like items illustrated in earliernumbered figures.

FIG. 2 shows a schematic illustrating elements of another prior art GCIBprocessing apparatus 200 for workpiece processing using a GCIB, whereinscanning of the ion beam and manipulation of the workpiece is employed.A workpiece 160 to be processed by the GCIB processing apparatus 200 isheld on a workpiece holder 202, disposed in the path of the GCIB 128. Inorder to accomplish uniform processing of the workpiece 160, theworkpiece holder 202 is designed to manipulate workpiece 160, as may berequired for uniform processing.

Any workpiece surfaces that are non-planar, for example, spherical orcup-like, rounded, irregular, or other un-flat configuration, may beoriented within a range of angles with respect to the beam incidence toobtain optimal GCIB processing of the workpiece surfaces. The workpieceholder 202 can be fully articulated for orienting all non-planarsurfaces to be processed in suitable alignment with the GCIB 128 toprovide processing optimization and uniformity. More specifically, whenthe workpiece 160 being processed is non-planar, the workpiece holder202 may be rotated in a rotary motion 210 and articulated inarticulation motion 212 by an articulation/rotation mechanism 204. Thearticulation/rotation mechanism 204 may permit 360 degrees of devicerotation about longitudinal axis 206 (which is coaxial with the axis 154of the GCIB 128) and sufficient articulation about an axis 208perpendicular to axis 206 to maintain the workpiece surface to within adesired range of beam incidence.

Under certain conditions, depending upon the size of the workpiece 160,a scanning system may be desirable to produce uniform irradiation of alarge workpiece. Although often not necessary for GCIB processing, twopairs of orthogonally oriented electrostatic scan plates 130 and 132 maybe utilized to produce a raster or other scanning pattern over anextended processing area. When such beam scanning is performed, a scangenerator 156 provides X-axis scanning signal voltages to the pair ofscan plates 132 through lead pair 159 and Y-axis scanning signalvoltages to the pair of scan plates 130 through lead pair 158. Thescanning signal voltages are commonly triangular waves of differentfrequencies that cause the GCIB 128 to be converted into a scanned GCIB148, which scans the entire surface of the workpiece 160. A scannedbeam-defining aperture 214 defines a scanned area. The scannedbeam-defining aperture 214 is electrically conductive and iselectrically connected to the low-pressure vessel 102 wall and supportedby support member 220. The workpiece holder 202 is electricallyconnected via a flexible electrical lead 222 to a faraday cup 216 thatsurrounds the workpiece 160 and the workpiece holder 202 and collectsall the current passing through the defining aperture 214. The workpieceholder 202 is electrically isolated from the articulation/rotationmechanism 204 and the faraday cup 216 is electrically isolated from andmounted to the low-pressure vessel 102 by insulators 218. Accordingly,all current from the scanned GCIB 148, which passes through the scannedbeam-defining aperture 214 is collected in the faraday cup 216 and flowsthrough electrical lead 224 to the dose processor 170. In operation, thedose processor 170 opens the beam gate 172 to initiate GCIB irradiationof the workpiece 160. The dose processor 170 typically integrates GCIBelectrical current arriving at the workpiece 160 and workpiece holder202 and faraday cup 216 to calculate an accumulated GCIB irradiationdose per unit area. At a predetermined dose, the dose processor 170closes the beam gate 172, terminating processing when the predetermineddose has been achieved. During the accumulation of the predetermineddose, the workpiece 160 may be manipulated by the articulation/rotationmechanism 204 to ensure processing of all desired surfaces.

FIG. 3 is a schematic of a Neutral Beam processing apparatus 300according to an embodiment of the invention, which uses electrostaticdeflection plates to separate the charged and uncharged portions of aGCIB. A beamline chamber 107 encloses the ionizer and acceleratorregions and the workpiece processing regions. The beamline chamber 107has high conductance and so the pressure is substantially uniformthroughout. A vacuum pump 146 b evacuates the beamline chamber 107. Gasflows into the beamline chamber 107 in the form of clustered andunclustered gas transported by the gas jet 118 and in the form ofadditional unclustered gas that leaks through the gas skimmer aperture120. A pressure sensor 330 transmits pressure data from the beamlinechamber 107 through an electrical cable 332 to a pressure sensorcontroller 334, which measures and displays pressure in the beamlinechamber 107. The pressure in the beamline chamber 107 depends on thebalance of gas flow into the beamline chamber 107 and the pumping speedof the vacuum pump 146 b. By selection of the diameter of the gasskimmer aperture 120, the flow of source gas 112 through the nozzle 110,and the pumping speed of the vacuum pump 146 b, the pressure in thebeamline chamber 107 equilibrates at a pressure, P_(B), determined bydesign and by nozzle flow. The GCIB flight path from grounded electrode144 to workpiece holder 162, is for example, 100 cm. By design andadjustment P_(B) may be approximately 6×10⁻⁵ torr (8×10⁻³ pascal). Thusthe product of pressure and beam path length is approximately 6×10⁻⁵torr (0.8 pascal-cm) and the gas target thickness for the beam isapproximately 1.94×10¹⁴ gas molecules per cm², which combined withmonomer evolution due to the initial ionization of the gas clusters inthe ionizer 122 and collisions that occur between gas cluster ions inthe GCIB 128 is observed to be effective for dissociating the gascluster ions in the GCIB 128 and results in a fully dissociatedaccelerated Neutral Beam 314. V_(Acc) may be for example 30 kV and theGCIB 128 is accelerated by that potential. A pair of deflection plates(302 and 304) is disposed about the axis 154 of the GCIB 128. Adeflector power supply 306 provides a positive deflection voltage V_(D)to deflection plate 302 via electrical lead 308. Deflection plate 304 isconnected to electrical ground by electrical lead 312 and throughcurrent sensor/display 310. Deflector power supply 306 is manuallycontrollable. V_(D) may be adjusted from zero to a voltage sufficient tocompletely deflect the ionized portion 316 of the GCIB 128 onto thedeflection plate 304 (for example a few thousand volts). When theionized portion 316 of the GCIB 128 is deflected onto the deflectionplate 304, the resulting current, I_(D) flows through electrical lead312 and current sensor/display 310 for indication. When V_(D) is zero,the GCIB 128 is undeflected and travels to the workpiece 160 and theworkpiece holder 162. The GCIB beam current I_(B) is collected on theworkpiece 160 and the workpiece holder 162 and flows through electricallead 168 and current sensor/display 320 to electrical ground. I_(B) isindicated on the current sensor/display 320. A beam gate 172 iscontrolled through a linkage 338 by beam gate controller 336. Beam gatecontroller 336 may be manual or may be electrically or mechanicallytimed by a preset value to open the beam gate 172 for a predeterminedinterval. In use, V_(D) is set to zero, and the beam current, I_(B),striking the workpiece holder is measured. Based on previous experiencefor a given GCIB process recipe, an initial irradiation time for a givenprocess is determined based on the measured current, I_(B). V_(D) isincreased until all measured beam current is transferred from I_(B) toI_(D) and I_(D) no longer increases with increasing V_(D). At this pointa Neutral Beam 314 comprising energetic dissociated components of theinitial GCIB 128 irradiates the workpiece holder 162. The beam gate 172is then closed and the workpiece 160 placed onto the workpiece holder162 by conventional workpiece loading means (not shown). The beam gate172 is opened for the predetermined initial radiation time. After theirradiation interval, the workpiece may be examined and the processingtime adjusted as necessary to calibrate the desired duration of NeutralBeam processing based on the measured GCIB beam current I_(B). Followingsuch a calibration process, additional workpieces may be processed usingthe calibrated exposure duration.

The Neutral Beam 314 contains a repeatable fraction of the initialenergy of the accelerated GCIB 128. The remaining ionized portion 316 ofthe original GCIB 128 has been removed from the Neutral Beam 314 and iscollected by the grounded deflection plate 304. The ionized portion 316that is removed from the Neutral Beam 314 may include monomer ions andgas cluster ions including intermediate size gas cluster ions. Becauseof the monomer evaporation mechanisms due to cluster heating during theionization process, intra-beam collisions, background gas collisions,and other causes (all of which result in erosion of clusters) theNeutral Beam substantially consists of neutral monomers, while theseparated charged particles are predominately cluster ions. Theinventors have confirmed this by suitable measurements that includere-ionizing the Neutral Beam and measuring the charge to mass ratio ofthe resulting ions. The separated charged beam components largelyconsist of cluster ions of intermediate size as well as monomer ions andperhaps some large cluster ions. As will be shown below, certainsuperior process results are obtained by processing workpieces usingthis Neutral Beam.

FIG. 4 is a schematic of a Neutral Beam processing apparatus 400according to an embodiment of the invention, which uses a thermal sensorfor Neutral Beam measurement. A thermal sensor 402 attaches via lowthermal conductivity attachment 404 to a rotating support arm 410attached to a pivot 412. Actuator 408 moves thermal sensor 402 via areversible rotary motion 416 between positions that intercept theNeutral Beam 314 or GCIB 128 and a parked position indicated by 414where the thermal sensor 402 does not intercept any beam. When thermalsensor 402 is in the parked position (indicated by 414) the GCIB 128 orNeutral Beam 314 continues along path 406 for irradiation of theworkpiece 160 and/or workpiece holder 162. A thermal sensor controller420 controls positioning of the thermal sensor 402 and performsprocessing of the signal generated by thermal sensor 402. Thermal sensor402 communicates with the thermal sensor controller 420 through anelectrical cable 418. Thermal sensor controller 420 communicates with adosimetry controller 432 through an electrical cable 428. A beam currentmeasurement device 424 measures beam current I_(B) flowing in electricallead 168 when the GCIB 128 strikes the workpiece 160 and/or theworkpiece holder 162. Beam current measurement device 424 communicates abeam current measurement signal to dosimetry controller 432 viaelectrical cable 426. Dosimetry controller 432 controls setting of openand closed states for beam gate 172 by control signals transmitted vialinkage 434. Dosimetry controller 432 controls deflector power supply440 via electrical cable 442 and can control the deflection voltageV_(D) between voltages of zero and a positive voltage adequate tocompletely deflect the ionized portion 316 of the GCIB 128 to thedeflection plate 304. When the ionized portion 316 of the GCIB 128strikes deflection plate 304, the resulting current I_(D) is measured bycurrent sensor 422 and communicated to the dosimetry controller 432 viaelectrical cable 430. In operation dosimetry controller 432 sets thethermal sensor 402 to the parked position 414, opens beam gate 172, setsV_(D) to zero so that the full GCIB 128 strikes the workpiece holder 162and/or workpiece 160. The dosimetry controller 432 records the beamcurrent I_(B) transmitted from beam current measurement device 424. Thedosimetry controller 432 then moves the thermal sensor 402 from theparked position 414 to intercept the GCIB 128 by commands relayedthrough thermal sensor controller 420. Thermal sensor controller 420measures the beam energy flux of GCIB 128 by calculation based on theheat capacity of the sensor and measured rate of temperature rise of thethermal sensor 402 as its temperature rises through a predeterminedmeasurement temperature (for example 70 degrees C.) and communicates thecalculated beam energy flux to the dosimetry controller 432 which thencalculates a calibration of the beam energy flux as measured by thethermal sensor 402 and the corresponding beam current measured by thebeam current measurement device 424. The dosimetry controller 432 thenparks the thermal sensor 402 at parked position 414, allowing it to cooland commands application of positive V_(D) to deflection plate 302 untilall of the current I_(D) due to the ionized portion of the GCIB 128 istransferred to the deflection plate 304. The current sensor 422 measuresthe corresponding I_(D) and communicates it to the dosimetry controller432. The dosimetry controller also moves the thermal sensor 402 fromparked position 414 to intercept the Neutral Beam 314 by commandsrelayed through thermal sensor controller 420. Thermal sensor controller420 measures the beam energy flux of the Neutral Beam 314 using thepreviously determined calibration factor and the rate of temperaturerise of the thermal sensor 402 as its temperature rises through thepredetermined measurement temperature and communicates the Neutral Beamenergy flux to the dosimetry controller 432. The dosimetry controller432 calculates a neutral beam fraction, which is the ratio of thethermal measurement of the Neutral Beam 314 energy flux to the thermalmeasurement of the full GCIB 128 energy flux at sensor 402. Undertypical operation, a neutral beam fraction of about 5% to about 95% isachieved. Before beginning processing, the dosimetry controller 432 alsomeasures the current, I_(D), and determines a current ratio between theinitial values of I_(B) and I_(D). During processing, the instantaneousI_(D) measurement multiplied by the initial I_(B)/I_(D) ratio may beused as a proxy for continuous measurement of the I_(B) and employed fordosimetry during control of processing by the dosimetry controller 432.Thus the dosimetry controller 432 can compensate any beam fluctuationduring workpiece processing, just as if an actual beam currentmeasurement for the full GCIB 128 were available. The dosimetrycontroller uses the neutral beam fraction to compute a desiredprocessing time for a particular beam process. During the process, theprocessing time can be adjusted based on the calibrated measurement ofI_(D) for correction of any beam fluctuation during the process.

FIG. 5 is a schematic of a Neutral Beam processing apparatus 500according to an embodiment of the invention that uses deflected ion beamcurrent collected on a suppressed deflection plate as a component of adosimetry scheme. Referring briefly to FIG. 4, the dosimetry schemeshown in FIG. 4 can suffer from the fact that the current, I_(D),includes the current due to the ionized portion 316 of the GCIB 128 aswell as secondary electron currents resulting from ejection of secondaryelectrons emitted when the ionized portion 316 of the beam strikesdeflection plate 304. The secondary electron yield can vary depending onthe distribution of cluster ion sizes in the ionized portion 316. It canalso vary depending on the surface state (cleanliness, etc.) of theimpacted surface of the deflection plate 304. Thus, in the schemedescribed in FIG. 4, the magnitude of I_(D) is not a preciserepresentation of the current due to the ionized portion 316 of the GCIB128. Referring again now to FIG. 5, an improved measurement of theionized portion 316 of GCIB 128 can be realized at deflection plate 304by adding an electron suppressor grid electrode 502 proximal to thesurface of deflection plate 304 that receives the ionized portion 316.The electron suppressor grid electrode 502 is highly transparent to theionized portion 316, but is biased negative with respect to thedeflection plate 304 by second suppressor voltage V_(S2) provided bysecond suppressor power supply 506. Effective suppression of secondaryelectrons is typically achieved by a V_(S2) on the order of several tensof volts. By suppressing the emission of secondary electrons, thecurrent loading of deflector power supply 440 is reduced and theprecision of the I_(D) representation of the current in the ionizedportion 316 of the GCIB 128 is increased. Electron suppressor grid 502is insulated from and maintained in proximity to deflection plate 304 byinsulating supports 504.

FIG. 6 is a schematic of a Neutral Beam processing apparatus 550according to an embodiment of the invention that uses a sample ofdeflected ion beam current collected in a faraday cup as a component ofa dosimetry scheme. In this embodiment of the invention, a sample 556 ofthe ionized portion 316 (as shown in FIG. 5) is captured in a faradaycup 558. Sample current, I_(S), collected in the faraday cup 558 isconducted via electrical lead 560 to current sensor 562 for measurement,and the measurement is communicated to a dosimetry controller 566 viaelectrical cable 564. Faraday cup 558 provides a superior currentmeasurement to that obtained by measuring the current I_(D) collected bydeflection plate 304 (as shown in FIG. 5). Current sensor 562 operatessubstantially as previously described for the current sensor 422 (asshown in FIG. 5) except that current sensor 562 has increasedsensitivity to accommodate the smaller magnitude of I_(S) as compared toI_(D). Dosimetry controller 566 operates substantially as previouslydescribed for dosimetry controller 432 (as shown in FIG. 5) except thatit is designed to accommodate a smaller current measurement I_(S) (ascompared to I_(D) of FIG. 5).

FIG. 7 is a schematic of a Neutral Beam processing apparatus 600according to an embodiment of the invention that uses mechanical scanner602 to scan a spatially extended workpiece 160 through the Neutral Beam314 to facilitate uniform Neutral Beam scanning of a large workpiece.Since the Neutral Beam 314 cannot be scanned by magnetic orelectrostatic techniques, when the workpiece 160 to be processed isspatially larger than the extent of the Neutral Beam 314 and uniformprocessing of the workpiece 160 is required, a mechanical scanner 602 isemployed to scan the workpiece 160 through the Neutral Beam 314.Mechanical scanner 602 has a workpiece holder 616 for holding workpiece160. The mechanical scanner 602 is disposed so that either the NeutralBeam 314 or the GCIB 128 can be incident on the workpiece 160 and/or theworkpiece holder 616. When the deflection plates (302, 304) deflect theionized portion 316 out of the GCIB 128, the workpiece 160 and/or theworkpiece holder 616 receive only the Neutral Beam 314. When thedeflection plates (302, 304) do not deflect the ionized portion 316 ofthe GCIB 128, the workpiece 160 and/or the workpiece holder 616 receivesthe full GCIB 128. Workpiece holder 616 is electrically conductive andis insulated from ground by insulator 614. Beam current (I_(B)) due toGLIB 128 incident on the workpiece 160 and/or the workpiece holder 616is conducted to beam current measurement device 424 via electrical lead168. Beam current measurement device 424 measures I_(S) and communicatesthe measurement to dosimetry controller 628. Mechanical scanner 602 hasan actuator base 604 containing actuators controlled by mechanical scancontroller 618 via electrical cable 620. Mechanical scanner 602 has aY-displacement table 606 capable of reversible motion in an Y-direction610, and it has an X-displacement table 608 capable of reversible motionin an X-direction 612, indicated as in and out of the plane of the paperof FIG. 7. Movements of the Y-displacement table 606 and of theX-displacement table 608 are actuated by actuators in the actuator base604 under control of the mechanical scan controller 618. Mechanical scancontroller 618 communicates via electrical cable 622 with dosimetrycontroller 628. Function of dosimetry controller 628 includes allfunctions previously described for dosimetry controller 432, withadditional function for controlling the mechanical scanner 602 viacommunication with mechanical scan controller 618. Based on measuredNeutral Beam energy flux rate, dosimetry controller 628 calculates andcommunicates to mechanical scan controller 618 the Y- and X-scanningrates for causing an integral number of complete scans of the workpiece160 to be completed during processing of a workpiece 160, insuringcomplete and uniform processing of the workpiece and insures apredetermined energy flux dose to the workpiece 160. Except for the useof a Neutral Beam, and the use of a Neutral Beam energy flux ratemeasurement, such scanning control algorithms are conventional andcommonly employed in, for examples, conventional GCIB processing toolsand in ion implantation tools. It is noted that the Neutral Beamprocessing apparatus 600 can be used as a conventional GCIB processingtool by controlling the deflection plates (302, 304) so that GCIB 128passes without deflection, allowing the full GCIB 128 to irradiate theworkpiece 160 and/or the workpiece holder 616.

FIG. 8 is a schematic of a Neutral Beam processing apparatus 700according to an embodiment of the invention that provides active settingand control of the gas pressure in the beamline chamber 107. A pressuresensor 330 transmits pressure measurement data from the beamline chamber107 through an electrical cable 332 to a pressure controller 716, whichmeasures and displays pressure in the beamline chamber. The pressure inthe beamline chamber 107 depends on the balance of gas flow into thebeamline chamber 107 and the pumping speed of the vacuum pump 146 b. Agas bottle 702 contains a beamline gas 704 that is preferably the samegas species as the source gas 112. Gas bottle 702 has a remotelyoperable leak valve 706 and a gas feed tube 708 for leaking beamline gas704 into the beamline chamber 107 through a gas diffuser 710 in thebeamline chamber 107. The pressure controller 716 is capable ofreceiving an input set point (by manual entry or by automatic entry froman system controller (not shown)) in the form of a pressure set point, apressure times beam path length set point (based on predetermined beampath length), or a gas target thickness set point. Once a set point hasbeen established for the pressure controller 716, it regulates the flowof beamline gas 704 into the beamline chamber 107 to maintain the setpoint during operation of the Neutral Beam processing apparatus. Whensuch a beamline pressure regulation system is employed, the vacuum pump146 b is normally sized so that in the absence of beamline gas 704 beingintroduced into the beamline chamber 107, the baseline pressure in thebeamline chamber 107 is lower than the desired operating pressure. Ifthe baseline pressure is chosen so that the conventional GCIB 12.8 canpropagate the length of the beam path without excessive dissociation,then the Neutral Beam processing apparatus 700 can also be used as aconventional GCIB processing tool.

FIG. 9 is a schematic of a Neutral Beam processing apparatus 800according to an embodiment of the invention that employs anelectrostatic mirror for separation of the charged and neutral beamportions. A reflecting electrode 802 and a substantially transparentelectrical grid electrode 804 are disposed displaced from each other,parallel to each other, and at a 45-degree angle to the beam axis 154.The reflecting electrode 802 and the substantially transparentelectrical grid electrode 804 both have holes (836 and 838 respectively)centered on the beam axis 154 for permitting passage of the Neutral Beam314 through the two electrodes. A mirror power supply 810 provides amirror electrical potential V_(M) across the gap between the reflectingelectrode 802 and the substantially transparent electrical gridelectrode 804 via electrical leads 806 and 808, with polarity asindicated in FIG. 9. V_(M) is selected to be slightly greater thanV_(Acc)+V_(R) (V_(R) being the retarding potential required to overcomethe thermal energy the gas cluster jet has before ionization andacceleration—V_(R) is typically on the order of a few kV). The electricfield generated between the reflecting electrode 802 and thesubstantially transparent electrical grid electrode 804 deflects theionized portion 814 of the GCIB 128 through approximately a 90-degreeangle with respect to the axis 154. A faraday cup 812 is disposed tocollect the ionized portion 814 of the GCIB 128. A suppressor electrodegrid electrode 816 prevents escape of secondary electrons from thefaraday cup 812. The suppressor grid electrode 816 is biased with anegative third suppressor voltage V_(S3) provided by third suppressorpower supply 822. V_(S3) is typically on the order of several tens ofvolts. The faraday cup current, I_(D2), representing current in thedeflected ionized portion 814 of the GCIB 128 (and thus the current inthe GCIB 128) flows through electrical lead 820 to current sensor 824.Current sensor 824 measures the current I_(D2) and transmits themeasurement to dosimetry controller 830 via electrical lead 826. Thefunction of dosimetry controller 830 is as previously described fordosimetry controller 432, except that dosimetry controller 830 receivesI_(D2) current measurement information from current sensor 824 anddosimetry controller 830 does not control deflector power supply 440,but instead controls mirror power supply 810 via electrical cable 840.By setting mirror power supply 810 to output either zero volts or V_(M),dosimetry controller 830 controls whether the full GCIB 128, or only theNeutral Beam 314 of GCIB 128 is transmitted to the workpiece 160 and/orworkpiece holder 616 for measurement and/or processing.

FIG. 10 is a schematic of a Neutral Beam processing apparatus 940according to an embodiment of the invention, which has the advantage ofboth the ionizer 122 and the workpiece 160 operating at groundpotential. The workpiece 160 is held in the path of Neutral Beam 314 byelectrically conductive workpiece holder 162, which in turn is supportedby electrically conductive support member 954 attached to a wall of thelow-pressure vessel 102. Accordingly, workpiece holder 162 and theworkpiece 160 are electrically grounded. An acceleration electrode 948extracts gas cluster ions from ionizer exit aperture 126 and acceleratesthe gas cluster ions through a voltage potential V_(Acc) provided byacceleration power supply 944 to form a GCIB 128. The body of ionizer122 is grounded and V_(Acc) is of negative polarity. Neutral gas atomsin the gas jet 118 have a small energy on the order of several tens ofmilli-electron-volts. As they condense into clusters, this energyaccumulates proportional to cluster size, N. Sufficiently large clustersgain non-negligible energies from the condensation process and whenaccelerated through a voltage potential of V_(Acc), the final energy ofeach ion exceeds V_(Acc) by its neutral cluster jet energy. Downstreamof the acceleration electrode 948, a retarding electrode 952 is employedto ensure deceleration of the ionized portion 958 of the GCIB 128.Retarding electrode 952 is biased at a positive retarding voltage,Y_(R), by retarding voltage power supply 942. A retarding voltage V_(R)of a few kV is generally adequate to ensure that all ions in the GCIB128 are decelerated and returned to the acceleration electrode 948.Permanent magnet arrays 950 are attached to the acceleration electrode948 to provide magnetic suppression of secondary electrons that wouldotherwise be emitted as a result of the returned ions striking theacceleration electrode 948. A beam gate 172 is a mechanical beam gateand is located upstream of the workpiece 160. A dosimetry controller 946controls the process dose received by the workpiece. A thermal sensor402 is placed into a position that intercepts the Neutral Beam 314 forNeutral Beam energy flux measurement or in the parked position forNeutral Beam processing of the workpiece under control of the thermalsensor controller 420. When thermal sensor 402 is in the beam sensingposition, the Neutral Beam energy flux is measured and transmitted tothe dosimetry controller 946 over electrical cable 956. In normal use,the dosimetry controller 946 closes the beam gate 172 and commands thethermal sensor controller 420 to measure and report the energy flux ofthe Neutral Beam 314. Next, a conventional workpiece loading mechanism(not shown) places a new workpiece on the workpiece holder. Based on themeasured Neutral Beam energy flux, the dosimetry controller 946calculates an irradiation time for providing a predetermined desiredNeutral Beam energy dose. The dosimetry controller 946 commands thethermal sensor 402 out of the Neutral Beam 314 and opens the beam gate172 for the calculated irradiation time and then closes the beam gate172 at the end of the calculated irradiation time to terminate theprocessing of the workpiece 160.

FIG. 11 is a schematic of a Neutral Beam processing apparatus 960according to an embodiment of the invention, wherein the ionizer 122operates at a negative potential Y_(R) and wherein the workpieceoperates at ground potential. An acceleration electrode 948 extracts gascluster ions from ionizer exit aperture 126 and accelerates the gascluster ions toward a potential of V_(Acc) provided by accelerationpower supply 944 to form a GCIB 128. The resulting GCIB 128 isaccelerated by a potential V_(Acc)−V_(R). A ground electrode 962decelerates the ionized portion 958 of the GCIB 128 and returns it tothe acceleration electrode 948.

FIG. 14 is a schematic of a Neutral Beam processing apparatus 980according to an embodiment of the invention. This embodiment is similarto that shown in FIG. 8, except that the separation of the charged beamcomponents from the neutral beam components is done by means of amagnetic field, rather than an electrostatic field. Referring again toFIG. 14, a magnetic analyzer 982 has magnetic pole faces separated by agap in which a magnetic B-field is present. Support 984 disposes themagnetic analyzer 982 relative to the GCIB 128 such that the GCIB 128enters the gap of the magnetic analyzer 982 such that the vector of theB-field is transverse to the axis 154 of the GCIB 128. The ionizedportion 990 of the GCIB 128 is deflected by the magnetic analyzer 982. Abaffle 986 with a Neutral Beam aperture 988 is disposed with respect tothe axis 154 so that the Neutral Beam 314 can pass through the NeutralBeam aperture 988 to the workpiece 160. The ionized portion 990 of theGCIB 128 strikes the baffle 986 and/or the walls of the low-pressurevessel 102 where it dissociates to gas that is pumped away by the vacuumpump 146 b.

FIGS. 12A through 12D show the comparative effects of full and chargeseparated beams on a gold thin film. In an experimental setup, a goldfilm deposited on a silicon substrate was processed by a full GCIB(charged and neutral components), a Neutral Beam (charged componentsdeflected out of the beam), and a deflected beam comprising only chargedcomponents. All three conditions are derived from the same initial GCIB,a 30 kV accelerated Ar GCIB. Gas target thickness for the beam pathafter acceleration was approximately 2×10¹⁴ argon gas atoms per cm². Foreach of the three beams, exposures were matched to the total energycarried by the full beam (charged plus neutral) at an ion dose of 2×10¹⁵gas cluster ions per cm². Energy flux rates of each beam were measuredusing a thermal sensor and process durations were adjusted to ensurethat each sample received the same total thermal energy dose equivalentto that of the full (charged plus neutral) GCIB dose.

FIG. 12A shows an atomic force microscope (AFM) 5 micron by 5 micronscan and statistical analysis of an as-deposited gold film sample thathad an average roughness, Ra, of approximately 2.22 nm. FIG. 12B showsan AFM scan of the gold surface processed with the full GCIB—averageroughness, Ra, has been reduced to approximately 1.76 nm. FIG. 12C showsan AFM scan of the surface processed using only charged components ofthe beam (after deflection from the neutral beam components)—averageroughness, Ra, has been increased to approximately 3.51 ran. FIG. 12Dshows an AFM scan of the surface processed using only the neutralcomponent of the beam (after charged components were deflected out ofthe Neutral Beam)—average roughness. Ra, is smoothed to approximately1.56 nm. The full GCIB processed sample (B) is smoother than the asdeposited film (A). The Neutral Beam processed sample (D) is smootherthan the full GCIB processed sample (B). The sample (C) processed withthe charged component of the beam is substantially rougher than theas-deposited film. The results support the conclusion that the neutralportions of the beam contribute to smoothing and the charged componentsof the beam contribute to roughening.

FIGS. 13A and 13B show comparative results of full GCIB and Neutral Beamprocessing of a drug film deposited on a cobalt-chrome coupon used toevaluate drug elution rate for a drug eluting coronary stent. FIG. 13Arepresents a sample irradiated using an argon GCIB (including thecharged and neutral components) accelerated using V_(Acc), of 30 kV withan irradiated dose of 2×10 cluster ions per cm². FIG. 13B represents asample irradiated using a Neutral Beam derived from an argon GCIBaccelerated using V_(Acc) of 30 kV. The Neutral Beam was irradiated witha thermal energy dose equivalent to that of a 30 kV accelerated, 2×10¹⁵gas cluster ion per cm² dose (equivalent determined by beam thermalenergy flux sensor). The irradiation for both samples was performedthrough a cobalt chrome proximity mask having an array of circularapertures of approximately 50 microns diameter for allowing beamtransmission. FIG. 13A is a scanning electron micrograph of a 300 micronby 300 micron region of the sample that was irradiated through the maskwith full beam. FIG. 13B is a scanning electron micrograph of a 300micron by 300 micron region of the sample that was irradiated throughthe mask with a Neutral Beam. The sample shown in FIG. 13A exhibitsdamage and etching caused by the full beam where it passed through themask. The sample shown in FIG. 13B exhibits no visible effect. Inelution rate tests in physiological saline solution, the samplesprocessed like the FIG. 13B sample (but without mask) exhibited superior(delayed) elution rate compared to the samples processed like the FIG.13A sample (but without mask). The results support the conclusion thatprocessing with the Neutral Beam contributes to the desired delayedelution effect, while processing with the full GCIB (charged plusneutral components) contributes to weight loss of the drug by etching,with inferior (less delayed) elution rate effect.

To further illustrate the ability of an accelerated Neutral Beam derivedfrom an accelerated GCIB to aid in attachment of a drug to a surface andto provide drug modification in such a way that it results in delayeddrug elution, an additional test was performed. Silicon couponsapproximately 1 cm by 1 cm (1 cm2) were prepared from highly polishedclean semiconductor-quality silicon wafers for use as drug depositionsubstrates. A solution of the drug Rapamycin (Catalog number R-5000, LCLaboratories, Woburn, Mass. 01801, USA) was formed by dissolving 500 mgof Rapamycin in 20 ml of acetone. A pipette was then used to dispenseapproximately 5 micro-liter droplets of the drug solution onto eachcoupon. Following atmospheric evaporation and vacuum drying of thesolution, this left approximately 5 mm diameter circular Rapamycindeposits on each of the silicon coupons. Coupons were divided intogroups and either left un-irradiated (controls) or irradiated withvarious conditions of Neutral Beam irradiation. The groups were thenplaced in individual baths (bath per coupon) of human plasma for 4.5hours to allow elution of the drug into the plasma. After 4.5 hours, thecoupons were removed from the plasma baths, rinsed in deionized waterand vacuum dried. Weight measurements were made at the following stagesin the process: 1) pre-deposition clean silicon coupon weight; 2)following deposition and drying, weight of coupon plus deposited drug;3) post-irradiation weight; and 4) post plasma-elution and vacuum dryingweight. Thus for each coupon the following information is available: 1)initial weight of the deposited drug load on each coupon; 2) the weightof drug lost during irradiation of each coupon; and 3) the weight ofdrug lost during plasma elution for each coupon. For each irradiatedcoupon it was confirmed that drug loss during irradiation wasnegligible. Drug loss during elution in human plasma is shown inTable 1. The groups were as follows: Control Group—no irradiation wasperformed; Group 1—irradiated with a Neutral Beam derived from a GCIBaccelerated with a V_(Acc) of 30 kV. The Group 1 irradiated beam energydose was equivalent to that of a 30 kV accelerated, 5×10¹⁴ gas clusterion per cm² dose (energy equivalence determined by beam thermal energyflux sensor); Group 2—irradiated with a Neutral Beam derived from a GCIBaccelerated with a V_(Acc) of 30 kV. The Group 2 irradiated beam energydose was equivalent to that of a 30 kV accelerated, 1×10¹⁴ gas clusterion per cm² dose (energy equivalence determined by beam thermal energyflux sensor); and Group 3—irradiated with a Neutral Beam derived from aGCIB accelerated with a V_(Acc) of 25 kV. The Group 3 irradiated beamenergy dose was equivalent to that of a 25 kV accelerated, 5×10¹⁴ gascluster ion per cm² dose (energy equivalence determined by beam thermalenergy flux sensor).

TABLE 1 Group Group 1 Group 2 Group 3 [Dose] [5 × 10¹⁴] [1 × 10¹⁴] [5 ×10¹⁴] {V_(Acc)} Control {30 kV} {30 kV} {25 kV} Start Elution ElutionStart Elution Elution Start Elution Start Elution Elution Coupon LoadLoss Loss Load Loss Loss Load Loss Loss Load Loss Loss # (μg) (μg) %(μg) (μg) % (μg) (μg) % (μg) (μg) % 1 83 60 72 88 4 5 93 10 11 88 — 0 287 55 63 100 7 7 102 16 16 82 5 6 3 88 61 69 83 2 2 81 35 43 93 1 1 4 9672 75 — — — 93 7 8 84 3 4 Mean 89 62 70 90 4 5 92 17 19 87 2 3 σ 5 7 9 39 13 5 2 p value 0.00048 0.014 0.00003

Table 1 shows that for every case of Neutral Beam irradiation (Groups 1through 3), the drug lost during a 4.5-hour elution into human plasmawas much lower than for the un-irradiated Control Group. This indicatesthat the Neutral Beam irradiation results in better drug adhesion and/orreduced elution rate as compared to the un-irradiated drug. The p values(heterogeneous unpaired T-test) indicate that for each of the NeutralBeam irradiated Groups 1 through 3, relative to the Control Group, thedifference in the drug retention following elution in human plasma wasstatistically significant.

FIGS. 15A through 15C show the comparative effects of full beam (chargedplus uncharged components) and charge separated beam on a single crystalsilicon wafer as may be typically employed in semiconductorapplications. The silicon substrate had an initial native oxide layer ofapproximately 1.3 nm. In separate instances, the silicon substrate wasprocessed using a full GCIB (charged and neutral components), a NeutralBeam derived from a GCIB (charged components removed from the beam bydeflection), and a charged cluster beam comprising only the chargedcomponents of a GCIB following their separation from the neutralcomponents. All three conditions were derived from the same initial GCIBconditions, a 30 kV accelerated GCIB formed from a mixture of 98% Arwith 2% O₂. For each of the three beams, irradiated doses were matchedto the total energy carried by the full beam (charged plus neutral) atan ion dose of 2×10¹⁵ gas cluster ions per cm². Energy flux rates ofeach beam were measured using a thermal sensor and process durationswere adjusted to ensure that each sample received the same total thermalenergy dose equivalent to that of the full (charged plus neutral) GCIB.The three samples were evaluated by sectioning followed by imaging bytransmission electron microscopy (TEM).

FIG. 15A is a TEM image 1000 of a section of a silicon substrateirradiated by the full GCIB (charged and neutral beam components). Theirradiation was incident on the silicon substrate from the direction ofthe top of the image toward the bottom of the image. Prior to sectioningfor TEM imaging, the top surface (irradiated surface) of the siliconsubstrate was coated with an epoxy overcoat to facilitate the sectioningoperation and to avoid damage to the substrate during the sectioningprocess. In the TEM image 1000, the epoxy overcoat 1006 is seen at thetop of the image. The irradiation formed an amorphous region 1004comprising silicon and oxygen having a minimum thickness ofapproximately 4.6 nm. A rough interface 1008 having a peak-to-peakvariation of approximately 4.8 nm was formed between the amorphousregion 1004 and the underlying single crystalline silicon 1002, as aresult of the irradiation process.

FIG. 15B is a TEM image 1020 of as section of a silicon substrateirradiated by the separated charged component of the GCIB (chargedportion only). The irradiation was incident on the silicon substratefrom the direction of the top of the image toward the bottom of theimage. Prior to sectioning for TEM imaging, the top surface (irradiatedsurface) of the silicon substrate was coated with an epoxy overcoat tofacilitate the sectioning operation and to avoid damage to the substrateduring the sectioning process. In the TEM image 1020, the epoxy overcoat1026 is seen at the top of the image. The irradiation formed anamorphous region 1024 comprising silicon and oxygen having a minimumthickness of approximately 10.6 nm. A rough interface 1028 having apeak-to-peak variation of approximately 5.9 mu was formed between theamorphous region 1024 and the underlying single crystalline silicon1022, as a result of the irradiation process.

FIG. 15C is a TEM image 1040 of a section of a silicon substrateirradiated by the neutral portion (charged components separated bydeflection and discarded). The irradiation was incident on the siliconsubstrate from the direction of the top of the image toward the bottomof the image. Prior to sectioning for TEM imaging, the top surface(irradiated surface) of the silicon substrate was coated with an epoxyovercoat to facilitate the sectioning operation and to avoid damage tothe substrate during the sectioning process. In the TEM image 1040, theepoxy overcoat 1046 is seen at the top of the image. The irradiationformed an amorphous region 1044 comprising silicon and oxygen having asubstantially uniform thickness of approximately 3.0 nm. A smoothinterface 1048 having a peak-to-peak variation on an atomic scale wasformed between the amorphous region 1044 and the underlying singlecrystalline silicon 1042, as a result of the irradiation process.

The results of processing shown in FIGS. 15A through 15C indicate thatin semiconductor applications, the use of an accelerated Neutral Beamderived from accelerated GCIB by charge separation results in superiorinterfaces between the irradiation processed and unprocessed regions ascompared to either a full GCIB or only the charged portion of a GCIB.The data also shows that a smooth uniform oxide film can be formed onsilicon using a Neutral Beam derived from a GCIB and that such film isfree of the rough interface often associated with the use ofconventional GCIB. Without wishing to be bound to a particular theory,it is believed that the improvement likely results from the eliminationof intermediate size clusters or from the elimination of all or mostclusters from the beam.

FIG. 16 is a graph 1060 showing results of secondary ion massspectrometry (SIMS) depth profile measurement of a shallow boronimplantation in a silicon substrate preformed using a Neutral Beamaccording to an embodiment the invention. The graph plots boronconcentration 1062 measured in boron atoms/cc (atoms/cm³) as a functionof depth measured in nm. Using apparatus similar to that shown in FIG.4, a 30 kV accelerated GCIB was formed from a mixture of 99% Ar with 1%diborane (B₂H₆). Stagnation chamber pressure was 80 psi (5.5×10⁵pascal), nozzle flow was 200 standard cm³/minute (3.3 standard cm³/sec).Full beam current (charged plus neutral components prior to separationby deflection was approximately 0.55 microA (μA). The pressure in thebeam path was maintained at approximately 6.9×10⁻⁵ torr (9.2×10⁻³pascal) and the background gas forming that pressure was essentiallyargon/diborane. The argon/diborane gas target thickness for the regionbetween the accelerator and the workpiece was approximately 2.23×10¹⁴gas monomers/cm², and the accelerated Neutral Beam was observed toconsist essentially of fully dissociated neutral monomers at the target.Using electrostatic deflection, all charged particles were deflectedaway from the beam axis and out of the beam, forming the essentiallyfully dissociated Neutral Beam. Thus the Neutral Beam was an acceleratedmonomer neutral argon/diborane beam. Dosimetry was done using a thermalsensor to calibrate the total Neutral Beam dose delivered to the siliconsubstrate such that a Neutral Beam deposited energy equivalent to thatenergy which would be deposited by a 6.3×10¹⁴ gas cluster ions/cm²irradiation dose by an accelerated (30 kV) GCIB including both thecharged and uncharged particles (without neutralization by chargeseparation). The depth profile shown in FIG. 16 indicates that theNeutral Beam boron ion implantation resulting from using a Neutral Beamderived from a. GCM, results in a very shallow boron implantation. Thejunction depth estimated from the 10¹⁸ boron atoms/cm³ concentrationdepth occurs at about 12 nm depth, a very shallow junction. Integratingthe boron dose over depth indicates an areal density of approximately7.94×10¹⁴ boron atoms/cm².

FIG. 17 is a TEM image 1100 of a section of a silicon substrateirradiated by the neutral portion (charged components separated bydeflection and discarded) derived from a GCIB. Using apparatus similarto that shown in FIG. 4, a 30 kV accelerated GCIB was formed from amixture of 99% Ar with 1% diborane (B₂H₆). Stagnation chamber pressurewas 88 psi (6.05×10⁵ pascal), nozzle flow was 200 standard cm³/minute(3.3 standard cm³/sec). Full beam current (charged plus neutralcomponents prior to separation by deflection was approximately 0.55microA (μA). The pressure in the beam path was maintained atapproximately 6.8×10⁻⁵ torr (9.07×10⁻³ pascal) and the background gasforming that pressure was essentially argon/diborane. The argon/diboranegas target thickness for the region between the accelerator exitaperture and the workpiece was therefore approximately 2.2×10¹⁴argon/diborane gas monomers/cm², and the accelerated Neutral Beam wasobserved to consist essentially of fully dissociated neutral monomers atthe target. Using electrostatic deflection all charged particles weredeflected away from the beam axis and out of the beam, forming a NeutralBeam, which was essentially fully dissociated. Thus the Neutral Beam wasan accelerated monomer neutral argon/diborane beam. Dosimetry was doneusing a thermal sensor to calibrate the total Neutral Beam dosedelivered to the silicon substrate such that a Neutral Beam depositedenergy equivalent to that energy which would be deposited by a 1.8×10¹⁴gas cluster ions/cm² irradiation dose by an accelerated (30 kV) GCIBincluding both the charged and uncharged particles (withoutneutralization by charge separation). The irradiation was incident onthe silicon substrate from the direction of the top of the image towardthe bottom of the image. Prior to sectioning for TEM imaging, the topsurface (irradiated surface) of the silicon substrate was coated with anepoxy overcoat to facilitate the sectioning operation and to avoiddamage to the substrate during the sectioning process. Referring againto FIG. 17, in the TEM image 1100, the epoxy overcoat 1106 is seen atthe top of the image. The irradiation formed an amorphous region 1104comprising silicon and boron having a substantially uniform thickness ofapproximately 1.9 nm. A smooth interface 1108 having a peak-to-peakvariation on an atomic scale was formed between the amorphous region1104 and the underlying single crystalline silicon 1102, as a result ofthe irradiation process. Prior art GCIB irradiation of semiconductormaterials for introducing dopants, strain inducing species, etc. areknown to form rougher interfaces between the processed film and theunderlying substrate, similar to the interface 1008 shown in FIG. 15A.It is shown that diborane can be employed to effectively dope asemiconductor with boron, with a high quality interface between thedoped film and the underlying substrate. By using other gases containingother dopant and/or lattice-straining species, species for increasingthe solid solubility limit of a dopant, or species for promoting surfaceamorphization, high quality films with superior interfaces between filmand substrate may be obtained as compared to conventional GCIBtechnology, where the presence of intermediate-sized cluster ions in thebeam may result in a rough interface. Some dopant containing gases thatmay be employed alone or in mixtures for introducing dopants are,diborane (B₂H₆), boron trifluoride (BF₃), phosphine (PH₃), phosphorouspentafluoride (PF₅), arsine (AsH₃), and arsenic pentafluoride (AsF₅), asexamples without limitation, may be employed for incorporating dopantatoms into gas dusters. Some gases that may be employed alone or inmixtures for introducing lattice-straining species are germane (GeH₄),germanium tetrafluoride (GeF₄), silane (SiH₁), silicon tetrafluoride(SiF₄), methane, (CH₄). Some gases that may be employed alone or inmixtures for promoting amorphization are, without limitation, argon(Ar), germane (GeH₄), germanium tetrafluoride (GeF₄), and fluorine (F₂).Some gases that may be employed alone or in mixtures for promotingdopant solubility are germane (GeH₄) and germanium tetrafluoride (GeF₄).Dopant-containing gases, gases containing lattice-straining species,gases containing amorphizing species, and/or gases containing speciesfor improving dopant solubility (and optionally inert or other gases)may be employed in mixtures for simultaneous formation of combinationsof benefits by the accelerated Neutral Beam process. In FIG. 17, thelead line connecting the numeric designator 1108 to its object changescolor to maintain contrast on regions in the figure having differingbackgrounds.

FIG. 18 illustrates a depth profile measurement graph 1200 obtainedafter using an accelerated Neutral Beam derived from a GCIB to etch asilicon dioxide (SiO₂) film on a silicon substrate and to etch thesilicon substrate. Using apparatus similar to that shown in FIG. 4, a 30kV accelerated GCIB was formed using argon. Stagnation chamber pressurewas 28 psi (1.93×10⁵ pascal), nozzle flow was 200 standard cm³/minute(3.3 standard cm³/sec). Full beam current (charged plus neutralcomponents prior to separation by deflection was approximately 0.50microA (μA). The argon gas target thickness for the region between theaccelerator and the workpiece was approximately 1.49×10¹⁴ argon gasmonomers/cm², and the accelerated Neutral Beam was observed to consistessentially of fully dissociated neutral monomers at the target. Usingelectrostatic deflection all charged particles were deflected away fromthe beam axis and out of the beam, forming a Neutral Beam. Thus theNeutral Beam was essentially an accelerated neutral argon monomer beam.Dosimetry was done using a thermal sensor to calibrate the total NeutralBeam dose delivered to the silicon substrate such that a Neutral Beamdeposited energy equivalent to that energy which would be deposited by a2.16×10¹⁶ gas cluster ions/cm² irradiation dose by an accelerated (30kV) GCIB including both the charged and uncharged particles (withoutneutralization by charge separation). A silicon dioxide (SiO₂) film(approximately 0.5 micron [μm] thick) on a silicon substrate waspartially masked with a narrow (approximately 0.7 mm wide) strip ofpolyimide film tape and then irradiated with the accelerated NeutralBeam. Following the irradiation the polyimide tape was removed.Referring again to FIG. 18, the depth profile measurement graph 1200 wasgenerated using a TENCOR Alpha-Step 250 profilometer to measure the stepprofile, in a direction along the surface of the SiO₂ film (on siliconsubstrate) and across the region masked by the polyimide film tape, dueto the etching resulting from the accelerated Neutral Beam. Plateau 1202represents the unetched surface of the SiO₂ film beneath the polyimidefilm (after film removal and cleaning), while the regions 1204 representthe etched portion. The accelerated Neutral Beam produced an etch depthof approximately 2.4 microns (μm), etching all the way through the 0.5micron SiO₂ film and an additional 1.9 microns into the underlyingcrystalline silicon substrate, producing the step shown in depth profilemeasurement graph 1200. Argon and other inert gases may be used assource gases to etch by physical means. By using a reactive source gasor using a source gas incorporating a reactive gas in a mixture,reactive etching can also be performed using a Neutral Beam. Typicalreactive gases that may be used alone or in mixture with inert gases are(without limitation) oxygen (O₂), carbon dioxide (CO₂), nitrogen (N₂),ammonia (NH₃), fluorine (F₂), chlorine (Cl₂), sulfur hexafluoride (SF₆),tetrafluoromethane (CF₄), and other condensable halogen-containinggases.

FIGS. 19A and 19B are TEM images illustrating production of amorphouslayers in crystalline semiconductor material by irradiating withaccelerated Neutral Beams derived from GCIBs. Prior to sectioning forTEM imaging, the top surface of each sample was coated with an epoxyovercoat to facilitate the sectioning operation and to avoid damage tothe surface during the sectioning process. Native oxide formsspontaneously in air or water when bare silicon is exposed.

FIG. 19A is a TEM image 1220 of a section of a silicon substrate with afilm of native SiO₂. In the TEM image 1220, the epoxy overcoat 1226 isseen at the top of the image. A thin (approximately 1.3 nm) native oxidefilm 1224 is seen on the underlying silicon substrate 1222.

FIG. 19B is a TEM image 1240 showing results of irradiation of a siliconsubstrate by an accelerated argon Neutral Beam derived from a GCIB. Asilicon wafer having a native oxide film similar to that shown in FIG.19A was cleaned in 1% aqueous solution of hydrofluoric acid to removethe native oxide. The cleaned silicon substrate was irradiated using aNeutral Beam derived from a 30 kV accelerated GCIB (charged componentsremoved from the beam by deflection) formed from argon. The irradiateddose was matched in energy to the total energy carried by a full beam(charged plus neutral) at an ion dose of 5×10 gas-cluster ions per cm²by using a thermal sensor to match the total energy deposited by theNeutral Beam to that of the full 5×10¹⁴ gas-cluster ions per cm² beam.Referring again to FIG. 19B, the TEM image 1240 shows the epoxy overcoat1246, a 2.1 nm thick amorphous film 1244 in the surface of the siliconformed by the accelerated Neutral Beam irradiation, overlying thecrystalline silicon substrate material 1242. A smooth interface 1248having a peak-to-peak variation on an atomic scale was formed betweenthe amorphous film 1244 and the underlying crystalline silicon material1242, as a result of the irradiation process. This shows that the noblegas, argon (Ar), may be employed to form an amorphous layer in acrystalline semiconductor material. Some other gases (withoutlimitation) that may be used to form amorphous layers by employing themin formation of accelerated Neutral Beams for embodiments of theinvention include, xenon (Xe), germane (GeH₄), and germaniumtetrafluoride (GeF₄). Such source gases may be used alone or in mixtureswith argon or other noble gases. In FIG. 19B, the lead line connectingthe numeric designator 1248 to its object changes color to maintaincontrast on regions in the figure having differing backgrounds.

FIGS. 20A and 20B are TEM images illustrating the growth of an oxidefilm on silicon by the use of accelerated Neutral Beams derived fromGCIBs. Prior to sectioning for TEM imaging, the top surface of eachsample was coated with an epoxy overcoat to facilitate the sectioningoperation and to avoid damage to the surface during the sectioningprocess.

FIG. 20A is a TEM image 1260 showing results of irradiation of a siliconsubstrate by an accelerated Neutral Beam derived from a GCIB. A siliconwafer having a native oxide film similar to that shown in FIG. 19A wascleaned in 1% aqueous solution of hydrofluoric acid to remove the nativeoxide. The cleaned, bare silicon substrate was then irradiated using aNeutral Beam derived from a 30 kV accelerated GCIB (charged componentsremoved from the beam by deflection) formed from a source gas mixture of98% Ar with 2% O₂. The irradiated Neutral Beam dose was energeticallyequivalent (energy equivalence determined by beam thermal energy fluxsensor) to a 30 kV accelerated GCIB at an ion dose of 2.4×10¹³ gascluster ions per cm². Referring again to FIG. 20A, the TEM image 1260shows the epoxy overcoat 1266, a 2 nrn thick oxide film 1264 in thesurface of the silicon formed by the accelerated Neutral Beamirradiation, overlying the crystalline silicon substrate material 1262.A smooth interface 1268 having a peak-to-peak variation on an atomicscale was formed between the oxide film 1264 and the underlyingcrystalline silicon material 1262, as a result of the irradiationprocess. In FIG. 20A, the lead line connecting the numeric designator1268 to its object changes color to maintain contrast on regions in thefigure having differing backgrounds.

FIG. 20B is a TEM image 1280 showing results of irradiation of a siliconsubstrate by an accelerated Neutral Beam derived from a GCIB. A siliconwafer having a native oxide film similar to that shown in FIG. 19A wascleaned in 1% aqueous solution of hydrofluoric acid to remove the nativeoxide. The cleaned, bare silicon substrate was then irradiated using aNeutral Beam derived from a 30 kV accelerated GCIB (charged componentsremoved from the beam by deflection) formed from a source gas mixture of98% Ar with 2% O₂. The irradiated Neutral Beam dose was energeticallyequivalent (energy equivalence determined by beam thermal energy fluxsensor) to a 30 kV accelerated GCIB at an ion dose of 4.7×10¹⁴ gascluster ions per cm². Referring again to FIG. 20B, the TEM image 1280shows the epoxy overcoat 1286, a 3.3 nm thick oxide film 1284 in thesurface of the silicon formed by the accelerated Neutral Beamirradiation, overlying the crystalline silicon substrate material 1282.A smooth interface 1288 having a peak-to-peak variation on an atomicscale was formed between the oxide film 1284 and the underlyingcrystalline silicon material 1282, as a result of the irradiationprocess. This shows that a Neutral Beam comprising oxygen may beemployed to form an oxide layer at the surface of a semiconductormaterial. The thickness of the film grown may be varied by varying theirradiated dose. By using source gases comprising other reactive speciesin forming the accelerated Neutral Beam, other types of films may begrown on semiconductor or other surfaces, for examples (withoutlimitation), oxygen (O₂), nitrogen (N₂), or ammonia (NH₃), alone or inmixture with argon (Ar) or other noble gas may be employed. In FIG. 20B,the lead line connecting the numeric designator 1288 to its objectchanges color to maintain contrast on regions in the figure havingdiffering backgrounds.

FIG. 21 illustrates a depth profile measurement graph 1300 obtainedafter using an accelerated Neutral Beam derived from a GCIB to deposit adiamondlike carbon film on a silicon substrate. Using apparatus similarto that shown in FIG. 4, a 30 kV accelerated GCIB was formed using asource gas mixture of 10% methane (CH₄) with 90% argon. The acceleratedNeutral Beam was observed to consist essentially of fully dissociatedneutral monomers at the target. Using electrostatic deflection allcharged particles were deflected away from the beam axis and out of thebeam, forming a neutral methane/argon beam. Thus the Neutral Beam wasessentially an accelerated neutral methane/argon monomer beam. Dosimetrywas done using a thermal sensor to calibrate the total Neutral Beamdelivered to the silicon substrate such that the Neutral Beam depositedenergy equivalent to that energy which would be deposited by a 2.8microA gas duster ions/cm² irradiation dose by an accelerated (30 kV)GCIB, including both the charged and uncharged particles (withoutneutralization by charge separation). A silicon substrate was partiallymasked with a narrow (approximately 1 mm wide) strip of polyimide filmtape and then the substrate and mask were irradiated with theaccelerated Neutral Beam for 30 minutes, depositing a diamond-likecarbon film. Following irradiation the mask was removed. Referring againto FIG. 21, the depth profile measurement graph 1300 was generated usinga TENCOR Alpha-Step 250 profilometer to measure the step profile, in adirection along the surface of the silicon substrate and across theregion masked by the polyimide film tape, due to the depositionresulting from the accelerated Neutral Beam. Flat region 1302 representsthe original surface of the silicon substrate beneath the polyimide film(after film removal and cleaning), while the regions 1304 represent thedeposited diamond-like carbon portion. The accelerated Neutral Beamproduced a deposition thickness of approximately 2.2 microns (μm),producing the step shown in depth profile measurement graph 1300. Thedeposition rate was approximately 0.45 nm/sec for each microA/cm² ofGCIB current (the energetic equivalent, as determined by thermal sensoras mentioned above in this paragraph). In other tests, 5% mixture and7.5% mixtures of CH₄ in argon, gave similar results, but with lowerdeposition rates resulting from lower CH₄ percentage in the source gas.Selection of gas mixture and dose permit repeatable deposition of filmswith predetermined thicknesses. CH₄, alone or in mixture with argon orother noble gas is an effective source gas for depositing carbon usingan accelerated neutral monomer beam. Other typical gases that may beused alone or in mixture with inert gases for film deposition usingaccelerated neutral monomer beams are (without limitation) germane(GeH₄), germanium tetrafluoride (GeF₄), silane (SiB₄), and silicontetrafluoride (SiF₄).

FIG. 22 shows a typical map 1320 resulting from an atomic forcemicroscope (AFM) evaluation a 500 nm by 500 nm region of the surface ofa conventionally cleaned and polished sample of a borosilicate opticalglass (Corning type 0211) of a type commonly employed in applicationssuch as optical windows, display and/or touch-screen substrates,microscopy slides and coverslips, filters, and the like. The surface hasan average roughness, R_(A), equal to 0.27 nm and exhibits numerousasperities 1322 having a height on the order of a few nm. Totalpeak-to-valley deviations are on the order of about 4 nm or more.

Processing such a surface using an essentially fully dissociated NeutralBeam derived from an accelerated GCIB results in considerable smoothingand planarization, and reduces the total peak-to-valley deviation. Aconventionally cleaned and polished sample of Corning type 0211 opticalglass was irradiated using a Neutral Beam derived from a 30 kVaccelerated GCIB (charged components removed from the beam bydeflection) formed from an Argon source gas. The irradiated Neutral.Beam dose was energetically equivalent (energy equivalence determined bybeam thermal energy flux sensor) to a 30 kV accelerated GCIB (iCEB at anion dose of 1×10¹⁴ gas cluster ions per cm².

FIG. 23 shows a map 1340 resulting from an AFM evaluation a 500 nm by500 nm region of the surface of the Neutral Beam irradiated glass. Thesurface has an average roughness, R_(A), equal to 0.13 nm, approximatelyhalf the roughness of the unirradiated material. The surface isessentially free of asperities. Total peak-to-valley deviations are onthe order of about 2 nm, approximately half that of the unirradiatedoptical surface.

The use of an accelerated Neutral Beam derived from an accelerated GCIBby separation of charged components from uncharged components is shownto be capable of numerous applications in the field of semiconductorprocessing, with an added benefit that the interface between the layerformed by the irradiation and the underlying semiconductor is extremelysmooth and superior to results obtained by conventional GCIBirradiation.

Another optical application that benefits from GCIB or Neutral Beamprocessing is related to the problem of adhering an optical film onto anoptical substrate. Optical devices are commonly improved by coating themwith various thin films to enhance or improve performance. Such opticalfilms may be employed as protective coatings, anti-reflection coatings,high reflection coatings, or in combinations to produce dichoric thinfilm optical filters. The coatings may be thin metal films (for examplesaluminum or gold), dielectric films (for examples magnesium fluoride,calcium fluoride, or metal oxides), or may be conductive films toenhance anti-static properties or to serve as electrodes for display ortouch sensitive structures. Such thin film coatings are often depositedusing physical vapor deposition (PVD) techniques or other conventionaltechniques suitable for the purpose. A common problem is that such filmsoften do not form a strong interface with the substrate or subsequentlayers and thus may not be as well adhered as is desirable. A problemarises because the coatings applied by PVD and other conventionaltechniques often do not form strong bonds to the substrate materialsbecause of their dissimilarity with the substrate materials. GCIB orNeutral Beam processing may be employed to produce thin film coatings onoptical substrates (onto optical devices or over other optical coatings)that are much more strongly adhered than coatings applied by theconventional techniques. To achieve a higher adhesion performance, aGCIB or Neutral Beam may be used to convert an initial seed coating to astrongly integrated interface layer with the substrate, and then formthe final coating to the desired thickness on the interface layer.Although both GCIB and Neutral Beam may be employed in manycircumstances, in the cases where either the substrate or the coating isa dielectric or low conductivity material, the Neutral Beam is preferredbecause of the aforementioned advantages it has for avoiding damage dueto the charge transport inherent in ion beam processing. Both GCM andNeutral Beam processing achieve an enhanced adhesion of the coatingwithout significant subsurface damage as often occurs with conventionalmonomer ion beams.

FIGS. 24A through 24D are schematics illustrating steps in embodimentsof the invention for the formation of strongly adhered optical coatingson optical substrates using GCIB or Neutral Beam techniques. FIG. 24A isa schematic 1400 showing an optical substrate 1402, having a very thinfilm coating of an optical coating material, 1404 having been previouslyapplied by a conventional technique such as PVD. There is an interface1406 between the optical coating material 1404 and the optical substrate1402 that has conventional adhesion properties (which may be inadequatefor the intended application). The thickness of the substrate 1402 andthe optical coating material 1404 are not necessarily shown to scale.GCIBs and Neutral Beams have penetration characteristics dependent onthe beam source materials, the beam acceleration potentials used, andthe range of sizes of any clusters present in the beam (though in afully dissociated Neutral Beam, clusters are not present). DissociatedNeutral Beams may, for example, have penetration depths into a typicaloptical coating material on the order of from about 1 to 3 nm, whileGCIB and Neutral Beams containing clusters may have penetration depthson the order of from about 2 to 20 nm (all dependent on the coatingmaterial and beam parameters.) In the method of this embodiment of theinvention the thickness of the optical coating material 1404 is chosenso that a practical beam typical parameters will penetrate the entirethickness of the optical coating material 1404 and also penetrate ashort distance (on the order of 1 to a few urn) into the opticalsubstrate 1402.

FIG. 24B is a schematic 1410 showing irradiation of the optical coatingmaterial 1404 with a beam 1412, which is a GCIB or a Neutral Beam. Thebeam 1412 characteristics are selected in conjunction with the thicknessof the optical coating material 1404 so that it is assured that at leasta fraction of the particles in the beam 1412 incident on the opticalcoating material 1404 penetrate it entirely. Those that penetrate, passthrough the conventional interface 1406, and into the optical substrate1402 for a distance on the order of from about 1 to a few nm. Theirradiated GCIB dose or Neutral Beam dose is for example at least 5×10¹³ions per cm² of a for example 30 kV accelerated GCIB, or in the case ofa Neutral Beam, energetically equivalent (energy equivalence determinedby beam thermal energy flux sensor) to a for example 30 kV acceleratedGCIB having an ion dose of at least 5×10¹³ gas cluster ions per cm².

FIG. 24C is a schematic 1420 showing the structure which results fromthe irradiation described above. Interaction of the beam with the thinfilm of optical coating material 1404 drives atoms from the opticalcoating material 1404 into the optical substrate 1402, forming a mixtureregion 1422, wherein the atoms of the optical coating material 1404 andthe optical substrate 1402 are intimately mixed, with a concentrationgradient of optical coating material atoms being higher in the upperregions of the mixture region and approaching zero in the lower regionsof the mixture region. The similar atoms in the upper regions of themixture region 1422 facilitate a strong bond with the atoms of theoptical coating material 1404 resulting in the optical coating material1404 being much more strongly adhered to the optical substrate than inthe case of the conventional interface 1406 (shown in FIG. 4A). Thethickness of the optical coating material 1404, which is necessarilylimited in thickness to allow penetration of the beam to form themixture region 1422, may be too thin for the desired optical coatingproperties, in such case, a subsequent deposition of additional opticalcoating material is required to create the desired optical coatingproperties.

FIG. 24D is a schematic 1430 illustrating an additional deposited layerof optical coating material 1432 to increase the net thickness ofoptical coating material 1404 plus optical coating material 1432 to thethickness necessary for the desired optical effect. Material 1404 andmaterial 1432 are commonly the same material, though they could bedifferent materials, provided the two materials form a strong adhesionbetween themselves. In one case, the material 1404 may be dissimilar toboth the optical substrate material and the upper material 1432, but thematerial 1404 may be chosen to bond chemically with both the substrateand the upper material, whereas the upper material and the opticalsubstrate may have no inherent affinity for each other. In the case ofthe two materials (material 1404 and material 1432) being the same, thesimilarity of atoms typically results in much stronger adhesion betweenthe two layers than occurs for the conventional interface 1406 (whichwas shown in FIG. 24A.)

A further application that benefits from GCIB or Neutral Beam processingis related to the problem of atmospheric degradation of materials. Forexample optical and other devices commonly employ materials that havehighly desirable optical characteristics, but which suffer from alsohaving characteristics that make them susceptible to degradation whenexposed to ordinary atmospheric conditions. This limits their usefulnessor useful service lifetime or useful shelf life when it is not practicalto avoid atmospheric exposure. Such materials may degrade due to surfaceoxidation, absorption of atmospheric moisture, or due to other reactionof the material's surfaces at the atmospheric interface. A specificexample is the material, lithium triborate (LBO), LiB₃O₅, which is apreferred material for many non-linear optics (NLO) applications. In NLOapplications, LBO often outperforms other available materials, butsuffers from the disadvantage that it is hygroscopic and is degraded byabsorption of moisture from the atmosphere or other sources. This limitsthe effective lifetime of the material in many applications, or even inother applications where limited atmospheric shelf-life causesdegradation before the material is placed into service. Additive surfacecoatings have conventionally been employed reduce the rate of moistureabsorption by providing a moisture barrier. However these are not alwaysas effective as may be required, and especially in the case ofapplications where the optical power density is high (e.g. laserapplications), coatings may delaminate or otherwise degrade and looseeffectiveness with time. As described hereinabove, the adhesion of suchcoatings may be improved by employing the GCIB and accelerated NeutralBeam techniques previously disclosed for improving film adhesion.However, GM or accelerated Neutral Beam irradiation may also be employedto form a thin harrier that reduces surface reactivity and/or moisturesusceptibility. The irradiation-formed barrier may be used incombination with subsequently applied conventional barrier coatings, ifdesired. Although both. GCIB and Neutral Beam may be employed in manycircumstances, the material treated is either a dielectric or lowconductivity material, the Neutral Beam is preferred because of theaforementioned advantages it has for avoiding damage due to the chargetransport inherent in ion beam processing. LBO surfaces deterioraterapidly when exposed directly to typical ambient atmospheric conditions.Accelerated Neutral Beam irradiation of LBO surfaces significantlydelays such deterioration.

FIGS. 25A and 25B are atomic force micrograph maps of surfaces of anuntreated LBO optical component showing degradation due to atmosphericexposure.

FIG. 25A shows a surface of an uncoated LBO optical component that hasbeen (for less than one hour) exposed to a typical ambient laboratoryatmosphere in a conventionally air conditioned building. The map shows atypical one micron by one micron square region of the crystal. Thelinear trough-like features are residual scratches in the conventionallypolished surface. Numerous elevated bumps have appeared, indicative ofonset of surface degradation due to atmospheric exposure of thehygroscopic LBO material. The surface exhibits an average roughness, Ra,of approximately 0.30 nm.

FIG. 25B shows a typical one micron by one micron square region of thesame piece of LBO material after 100 hours of exposure to the sameambient laboratory atmosphere. The surface degradation is seen to haveprogressed substantially—average roughness, Ra, is increased toapproximately 3.58 nm, due to the increased areas and heights of thebumps growing on the surface.

FIGS. 26A and 26B are atomic force micrograph maps of surfaces of an LBOoptical component treated using an accelerated Neutral Beam derived froma GCIB, with resulting reduced degradation due to atmospheric exposure.

FIG. 26A shows a surface of the same piece of uncoated LBO opticalcomponent that was shown above in FIG. 25A. After brief (for less thanone hour) exposure to ambient laboratory atmosphere in a conventionallyair conditioned building, a portion of the surface was processed withaccelerated Neutral Beam irradiation. Following the irradiation step,the atomic force microscope image of part of the irradiated portionshown in FIG. 26A was measured. The map shows a typical one micron byone micron square region of the irradiated portion of the crystalimmediately after irradiation. The linear trough-like scratches are nolonger apparent and the surface exhibits an average roughness, Ra, ofapproximately 0.26 nm. The irradiated portion of the surface wasirradiated using a Neutral Beam derived from an argon GCIB acceleratedusing V_(Acc) of 30 kV. The Neutral Beam was irradiated with a neutralatom dose of 5×10¹⁸ argon atoms per cm². Other experiments have shownthat a neutral atom dose of as low as 2.5×10¹⁷ argon atoms per cm² iseffective (alternatively, effective GCIB doses have similar accelerationand a combination of cluster ion sizes and dose that provide a similardose of argon atoms).

FIG. 26B shows a typical one micron by one micron square region of thesame piece of LBO material after 100 hours of continued exposure to thesame ambient laboratory atmosphere. The surface degradation hasprogressed very little—average roughness, Ra, is approximately 0.29 nm.The Neutral Beam irradiation has resulted in a shallow surfacemodification that functions as a barrier to moisture absorption andperhaps other forms of degradation, extending the functionally usefullifetime of the hygroscopic. LBO optical material. At the end of 1.00hours of atmospheric exposure the irradiated surface appears of equal orbetter quality than that of the original material after just one hour ofatmospheric exposure.

Although embodiments of the invention have been described with respectto a hygroscopic LBO optical material, it is understood by the inventorsthat it is equally applicable to other hygroscopic crystalline materialsas may be employed in optical and other applications. For exampleshygroscopic thallium-doped sodium iodide crystals and slightlyhygroscopic thallium- or sodium-doped cesium iodide crystals are used ingamma ray scintillation spectroscopy and are subject to degradation dueto moisture absorption. Such degradation may be delayed or reduced byirradiation. Although the example described above utilized Neutral Beamirradiation of LBO, it is understood by the inventors that GCIBirradiation may also be applied effectively, though Neutral Beamirradiation is considered preferable in the case of materials having lowelectrical conductivity. It is also understood by the inventors thatprior to irradiation to reduce surface degradation of hygroscopicmaterials, it may be useful to use a pretreatment of GCIB or Neutralbeam to smooth the surface and remove existing surface degradation.

Although embodiments of the invention have been described with respectto silicon semiconductor materials, it is understood by the inventorsthat it is equally applicable to other semiconductor materials includinggermanium, and compound semiconductors including, without limitation,group III-V and group II-VI and related materials and it is intendedthat the scope of the invention is intended to include those materials.

It is understood by the inventors that although embodiments of theinvention has been shown for exemplary purposes to be useful forprocesses such a smoothing, etching, film growth, film deposition,amorphization, and doping by using silicon semiconductor wafers, it isunderstood by the inventors that the benefits of the invention are notlimited only to processes done on bare semiconductor surfaces, but areequally useful for processing portions of electrical circuits,electrical devices, optical elements, integrated circuits,micro-electrical mechanical systems (MEMS) devices (and portionsthereof) and other devices that are commonly constructed usingconventional modern technologies on silicon substrates, othersemiconductor substrates, and substrates of other materials, and it isintended that the scope of the invention includes such applications.

Although the benefits of applying the Neutral Beam of the invention forelectrical charging-free processing have been described with respect toprocessing various electrically insulating and/ornon-electrically-conductive materials such as insulating drug coatings,dielectric films such as oxides and nitrides, insulating corrosioninhibitor coatings, polymers, organic films, glasses, ceramics, it isunderstood by the inventors that all materials of poor or low electricalconductivity may benefit from using the Neutral Beam disclosed herein asa substitute for processing with charge transferring processingtechniques like ion beams, plasmas, etc., and it is intended that thescope of the invention includes such materials. It is further understoodby the inventors that Neutral Beam processing is advantageous not onlybecause of its reduced charging characteristics, but also for processingmany materials that are electrically conductive, where other advantagesof Neutral Beam processing, especially neutral monomer beam processing,which produces less surface damage, better smoothing, and smootherinterfaces between processed and underlying unprocessed regions, even inmetals and highly conductive materials. It is intended that the scope ofthe invention includes processing of such materials.

Although the benefits of applying the Neutral Beam disclosed herein forelectrical charging-free processing have been described with respect toprocessing various insulating and/or non-electrically-conductivematerials, it is understood by the inventors that the charge-freeNeutral Beam processing benefits apply equally to the processing ofelectrically conductive, semiconductive, or slightly conductivematerials that exist in the form of coatings or layers or other formsoverlying insulating layers or disposed upon insulating substrates,wherein the at least slightly conductive materials have no reliableground connection or other pathway for removing surface charges that maybe induced by processing using charge transferring processingtechniques. In such cases, charging of the at least slightly conductivematerials during processing may produce damage to those materials or tothe underlying insulating materials. The charging and damage may beavoided by using the Neutral Beam processing of the invention. It isintended by the inventors that the scope of the invention includesprocessing of such dissimilar material arrangements where an at leastslightly conductive material overlays an insulating material.

Although the benefits of applying the Neutral Beam of the invention forsmoothing optical materials have been described with respect toprocessing Corning type 0211 optical glass, an amorphous material it isunderstood by the inventors that the charge-free Neutral Beam processingbenefits apply equally to the processing other optical materials,amorphous or crystalline, including without limit, glasses, quartz,sapphire, diamond, and other hard, transparent optical materials (eitheremployed as optical elements or as gem [natural or synthetic]materials), it is further understood by the inventors that Neutral Beamprocessing may be used for also applying optical coatings to suchmaterials and for affecting optical characteristics of such materials,such as the refractive index. It is intended by the inventors that thescope of the invention includes processing of such materials for opticaland gem applications.

Although the invention has been described with respect to variousembodiments, it should be realized this invention is also capable of awide variety of further and other embodiments within the spirit andscope of the invention.

The invention claimed is:
 1. A method of treating a surface of anoptical element comprising the steps of: providing a reduced pressurechamber; forming a gas cluster ion beam comprising gas cluster ionswithin the reduced pressure chamber; accelerating and focusing the gascluster ions to form an accelerated and focused gas cluster ion beamalong a beam path within the reduced pressure chamber; promotingfragmentation and/or dissociation of the accelerated and focused gascluster ions along the beam path while substantially retaining the focusof the gas cluster ion-beam; removing charged particles from the beampath to form an accelerated and focused neutral beam along the beam pathin the reduced pressure chamber; holding the optical element in the beampath; treating at least a portion of a surface of the optical element byirradiating it with the accelerated and focused neutral beam; andwherein the promoting and removing steps occur prior to irradiating thesurface.
 2. The method of claim 1, wherein the step of removing removesessentially all charged particles from the beam path.
 3. The method ofclaim 1, wherein the neutral beam is substantially free of intermediatesized clusters having a few hundred to a few thousand atoms ormolecules.
 4. The method of claim 1, wherein the neutral beam consistsessentially of gas from the gas cluster ion beam.
 5. The method of claim1, wherein the step of promoting includes raising an accelerationvoltage in the step of accelerating or improving ionization efficiencyin the forming of the gas cluster ion beam.
 6. The method of claim 1,wherein the step of promoting includes increasing the range ofvelocities of ions in the accelerated gas cluster ion beam.
 7. Themethod of claim 1, wherein the step of promoting includes introducingone or more gaseous elements used in forming the gas cluster ion beaminto the reduced pressure chamber to increase pressure along the beampath.
 8. The method of claim 1, wherein the step of promoting includesincreasing the size of a skimmer aperture used in the step of formingthe gas cluster ion beam.
 9. The method of claim 1, wherein the step ofpromoting includes irradiating the accelerated gas cluster ion beam orthe neutral beam with radiant energy.
 10. The method of claim 1, whereinthe neutral beam treating at least a portion of a surface of theworkpiece consists substantially of monomers having an energy between 1eV and several thousand eV.
 11. The method of claim 1, furthercomprising the step of repositioning the workpiece with a workpieceholder to treat plural portions of the surface.
 12. The method of claim1, further comprising the step of scanning the workpiece with aworkpiece holder to treat extended portions of the surface.
 13. Themethod of claim 1, where the holding step introduces the optical devicethat comprises any of: an electrically insulating material; a highelectrical resistivity material; a crystalline material; an amorphousmaterial; a hygroscopic material; a glass material; a gem material;quartz; or a transparent material.
 14. The method of claim 1, whereinthe treating step forms an optical coating on the optical element. 15.The method of claim 1, wherein the treating step modifies an opticalproperty of the optical element.
 16. The method of claim 15, wherein theoptical property is a refractive index.
 17. The method of claim 1,wherein the optical element is a gem material.
 18. The method of claim17, wherein the gem material is selected from the group consisting ofdiamond, sapphire, quartz, or a synthetic gem material.
 19. The methodof claim 1, wherein the optical element comprises lithium triborate(LBO) and further wherein the treating step forms a surface barrier thatreduces reactivity or susceptibility to moisture degradation at thesurface of the LBO.
 20. The method of claim 19, wherein the forming stepfurther comprises forming a gas cluster ion beam comprising gas clusterions comprising methane.
 21. The method of claim 19, wherein thetreating step smoothens the at least a portion of the surface of the LBOto an RMS roughness less than 0.3 nm.
 22. The method of claim 1, whereinthe step of promoting fragmentation and/or dissociation of theaccelerated and focused gas cluster ion beam does not deflect theaccelerated and focused gas cluster ion beam.